TWI805781B - Resist composition and method of forming resist pattern - Google Patents

Abstract

A resist composition including a base component (A) and an acid generator component (B), the base component (A) including a resin component (A1) having a structural unit (a0) represented by general formula (a0) shown below, and the acid generator component (B) containing at least one member selected from the group consisting of a compound (b-1), a compound (b-2) and a compound (b-3) represented by general formula (b-3) shown below (wherein Wa represents a divalent aromatic hydrocarbon group; Ra⁰⁰ represents an acid dissociable group; R¹⁰¹ , R¹⁰⁴ and R¹⁰⁶ each independently represents a hydrocarbon group containing an aromatic ring; R¹⁰⁵ , R¹⁰⁷ and R¹⁰⁸ each independently represents a cyclic group, a chain alkyl group which may have a substituent or a chain alkenyl group; R¹⁰² represents a fluorine atom or a fluorinated alkyl group of 1 to 5 carbon atoms and M’^m+ represents an m-valent onium cation).

Description

Resist composition and resist pattern forming method

The present invention relates to a resist composition and a resist pattern forming method. In this case, priority is claimed based on Japanese Patent Application No. 2018-115625 filed in Japan on June 18, 2018, and its content is cited in the following description.

In lithographic etching technology, generally, for example, forming a resist film formed of a resist material on a substrate, selectively exposing the resist film, applying development treatment, etc., and forming on the aforementioned resist film Steps such as resist patterning of a specific shape are carried out. The resist material whose exposed part of the resist film changes to dissolve in the developing solution is called positive type, and the resist material whose exposed part changes to the property of not dissolving in the developing solution is called negative type. In recent years, in the manufacture of semiconductor elements or liquid crystal display elements, along with the advancement of lithographic etching technology, the miniaturization of patterns has rapidly entered. The method of miniaturization is generally carried out by shortening the wavelength (higher energy) of the exposure light source. Specifically, ultraviolet light represented by g-line and i-line has been used in the past, but now KrF excimer laser or ArF excimer laser is used for mass production of semiconductor devices. Furthermore, studies have also begun on EUV (extreme ultraviolet), EB (electron beam), X-rays, etc., which have a shorter wavelength (high energy) than these excimer lasers.

In addition, currently, in EUV lithography or EB lithography, resist materials are used for the purpose of improving the sensitivity to EUV or EB, and the resolution of fine resist patterns that can be used as targets, etc. , So far, chemically amplified resists proposed as KrF excimer lasers, ArF excimer lasers, etc. are generally used. In particular, the chemically amplified resist containing acrylic resin as the base resin can make these lithographic etching properties more excellent. In resist materials, especially in EUV exposure, acid diffusion control is mostly a problem to be solved. In the method of controlling the diffusion of acid, the method of changing the anion structure of the acid generator is generally used, so the anion structure known to have a short diffusion length of the acid is often used. Also, in relation to the control of acid diffusion, etc., various changes in the design of polymer compounds have been used.

For example, in Patent Document 1, it is described that a polymer compound having a specific acid-dissociative functional group is used to improve the reactivity to acid, the solubility to a developing solution, and the like as a resist composition. In Patent Document 2, it is described to use a polymer compound having a repeating unit having a styrene carboxylic acid skeleton, and the hydrogen atom of the hydroxyl group of the carboxyl group is replaced by an acid labile group, which can inhibit the diffusion of acid and improve the dissolution ratio and Etch-resistant resist composition. [Prior Art Literature] [Patent Document]

[Patent Document 1] International Publication No. 2010/095698 [Patent Document 2] Japanese Patent No. 4305637

[Problem to be solved by the invention]

With the advancement of lithographic etching technology, the development of finer resist patterns, such as lithographic etching using EUV or EB, all aim to form fine patterns of tens of nanometers. The smaller the size of the resist patterns, the higher the sensitivity to the exposure light source, and the good lithographic etching characteristics such as low roughness are required in the resist composition. From the point of view of improving the lithographic etching characteristics, there is still room for improvement, such as the addition of polymer compounds and acid generators in the resist composition.

The present invention is proposed in view of the above circumstances, and aims to provide a resist composition having good lithographic etching characteristics, and a resist pattern forming method using the resist composition. [How to solve the problem]

As a result of research, the present inventors found that the roughness of the resist pattern can be improved by controlling the diffusion of the acid generated by the exposure to the unexposed portion of the pattern (acid diffusion). In addition, the present inventors have found that effects such as diffusion of acid can be controlled by improving the interaction between the base resin of the resist and the acid generator, and thus completed the present invention.

The first aspect of the present invention is a resist composition that generates acid through exposure and changes the solubility of the developer through the action of the acid, which contains: The base material component (A) that changes the solubility of the developer due to the action of the developer, and the acid generator component (B) that generates acid through exposure, and the above base material component (A) contains the following general formula: The structural unit (a0) represented by (a0) is a resin component (A1), and the acid generator component (B) contains a compound (b-1) represented by the following general formula (b-1), the following general formula At least one selected from the group consisting of a compound (b-2) represented by formula (b-2) and a compound (b-3) represented by the following general formula (b-3).

[式中，R⁰ 為氫原子、碳數1～5之烷基、鹵素原子或碳數1～5之鹵化烷基；Va^x0 為單鍵或2價之連結基；Wa為可具有取代基的2價之芳香族烴基；Va⁰ 為可具有醚鍵結的2價之烴基；n_a0 為0～2之整數；Ra⁰⁰ 為酸解離性基]。

[wherein, R ⁰ is a hydrogen atom, an alkyl group with 1 to 5 carbons, a halogen atom or a halogenated alkyl group with 1 to 5 carbons; Va ^x0 is a single bond or a divalent linking group; Wa is an optional substituent 2-valent aromatic hydrocarbon group; Va ⁰ is a 2-valent hydrocarbon group that may have ether linkage; n _a0 is an integer from 0 to 2; Ra ⁰⁰ is an acid dissociative group].

[式中，R¹⁰¹ 、R¹⁰⁴ 及R¹⁰⁶ ，各別獨立為含有可具有取代基的芳香環之烴基；R¹⁰⁵ 、R¹⁰⁷ 及R¹⁰⁸ ，各別獨立為可具有取代基之環式基、可具有取代基之鏈狀烷基，或可具有取代基之鏈狀烯基；R¹⁰² 為氟原子或碳數1～5之氟化烷基。Y¹⁰¹ 為單鍵或含有氧原子的2價之連結基。 V¹⁰¹ ～V¹⁰³ 各別獨立為單鍵、伸烷基或氟化伸烷基。L¹⁰¹ ～L¹⁰² 各別獨立為單鍵或氧原子。L¹⁰³ ～L¹⁰⁵ 各別獨立為單鍵、-CO-或-SO₂ -。m為1以上之整數，且M’^m+ 為m價之鎓陽離子]。

[wherein, R ¹⁰¹ , R ¹⁰⁴ and R ¹⁰⁶ are each independently a hydrocarbon group containing an aromatic ring that may have a substituent; R ¹⁰⁵ , R ¹⁰⁷ and R ¹⁰⁸ are each independently a cyclic group that may have a substituent, A chained alkyl group that may have a substituent, or a chained alkenyl group that may have a substituent; R ¹⁰² is a fluorine atom or a fluorinated alkyl group with 1 to 5 carbon atoms. ^Y101 is a single bond or a divalent linking group containing an oxygen atom. V ¹⁰¹ to V ¹⁰³ are each independently a single bond, an alkylene group or a fluorinated alkylene group. L ¹⁰¹ to L ¹⁰² are each independently a single bond or an oxygen atom. L ¹⁰³ to L ¹⁰⁵ are each independently a single bond, -CO- or -SO ₂ -. m is an integer of 1 or more, and M' ^m+ is an m-valent onium cation].

The second aspect of the present invention is a method for forming a resist pattern, comprising: using the resist composition of the first aspect to form a resist film on a support; exposing the resist film to light. step, and the step of developing the above-mentioned exposed resist film to form a resist pattern. [Effect of Invention]

According to the content of the present invention, a resist composition with good lithographic etching properties and a resist pattern forming method using the resist composition can be provided.

[Mode of Implementing the Invention]

In this specification and the claims of this application, "aliphatic" is a concept that is relative to aromatic, and is defined as a group, compound, etc. that do not have aromaticity. "Alkyl group" includes linear, branched and cyclic monovalent saturated hydrocarbon groups unless otherwise specified. The same applies to the alkyl group in the alkoxy group. The "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups unless otherwise specified. A "halogenated alkyl group" is a group in which a part or all of the hydrogen atoms of the alkyl group are replaced by a halogen atom. The halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A "fluorinated alkyl group" or "fluorinated alkylene group" is a group in which a part or all of the hydrogen atoms of the alkyl group or alkylene group are substituted with fluorine atoms. "Structural unit" means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer). The case described as "may have a substituent" includes the case where a hydrogen atom (-H) is substituted by a monovalent group, and the case where a methylene group (-CH ₂ -) is substituted by a divalent group, etc. By. "Exposure" is an overall concept including radiation exposure.

"Structural unit derived from acrylate" means a structural unit formed by cleavage of the ethylenic double bond of acrylate. "Acrylic ester" is a compound in which the hydrogen atom at the carboxyl terminal of acrylic acid (CH ₂ =CH-COOH) is substituted with an organic group. In acrylate, the hydrogen atom bonded to the carbon atom at the alpha position can be replaced by a substituent. The substituent (R ^α0 ) that replaces the hydrogen atom bonded to the carbon atom at the α position is an atom or group other than a hydrogen atom, such as: an alkyl group with 1 to 5 carbon atoms, a halogenated group with 1 to 5 carbon atoms Alkyl etc. Also includes itaconic acid diesters in which the substituent (R ^α0 ) is substituted by a substituent containing an ester bond, or in which the substituent (R ^α0 ) is substituted by a hydroxyalkyl group or a group obtained by modifying the hydroxyl group Alpha hydroxy acrylates. Also, the carbon atom at the α-position of the acrylate refers to the carbon atom to which the carbonyl group of acrylic acid is bonded, unless otherwise specified. Hereinafter, an acrylate obtained by substituting a hydrogen atom bonded to a carbon atom at the α position is also called an α-substituted acrylate. Also, acrylates and α-substituted acrylates are collectively referred to as “(α-substituted) acrylates”. Also, acrylic acid in which the hydrogen atom bonded to the carbon atom at the α position is replaced by a substituent is also called α-substituted acrylic acid. Also, acrylic acid and α-substituted acrylic acid are collectively referred to as "(α-substituted) acrylic acid".

"Structural unit derived from acrylamide" means a structural unit formed by cleavage of the ethylenic double bond of acrylamide. In acrylamide, the hydrogen atom bonded to the carbon atom at the α position may be replaced by a substituent, or one or both of the hydrogen atoms in the amine group of the acrylamide may be replaced by a substituent. Also, the carbon atom at the α-position of acrylamide means the carbon atom to which the carbonyl group of acrylamide is bonded unless otherwise specified. Substituents that substitute the hydrogen atom bonded to the carbon atom at the α-position of acrylamide, for example, are the same as those listed as the substituent at the α-position (substituent (R ^α0 )) in the above-mentioned α-substituted acrylate content etc.

"Structural unit derived from hydroxystyrene" means a structural unit formed by cleavage of the ethylenic double bond of hydroxystyrene. The "structural unit derived from a hydroxystyrene derivative" means a structural unit formed by cleavage of the ethylenic double bond of a hydroxystyrene derivative. "Hydroxystyrene derivatives" refers to those obtained by substituting the α-position hydrogen atom of hydroxystyrene with other substituents such as alkyl groups, halogenated alkyl groups, and the concepts of derivatives thereof. These derivatives include, for example: the hydrogen atom in the α-position can be replaced by a substituent; the hydrogen atom in the hydroxyl group of hydroxystyrene can be replaced by an organic group; the hydroxy group can be substituted by a substituent. Substituents other than hydroxyl groups bonded to the benzene ring of styrene, etc. Also, the α-position (carbon atom at the α-position) means the carbon atom bonded to the benzene ring unless otherwise specified. The substituents substituting the hydrogen atom at the α-position of hydroxystyrene are, for example, the same as those listed as the substituents at the α-position in the aforementioned α-substituted acrylate.

"Structural unit derived from ethylene benzoic acid or ethylene benzoic acid derivative" means a structural unit formed by cleavage of the ethylenic double bond of ethylene benzoic acid or ethylene benzoic acid derivative. "Ethylene benzoic acid derivatives" refers to those whose α-position hydrogen atoms of ethylene benzoic acid are replaced by other substituents such as alkyl groups, halogenated alkyl groups, and their derivatives. These derivatives include, for example: the hydrogen atom in the carboxyl group of ethylene benzoic acid that can be replaced by a substituent; the hydrogen atom in the α-position can be replaced by a substituent; Substituents other than hydroxyl and carboxyl are bonded to the benzene ring of benzoic acid. Also, the α-position (carbon atom at the α-position) means the carbon atom bonded to the benzene ring unless otherwise specified.

The above-mentioned alkyl group as the substituent at the α position is preferably a straight-chain or branched-chain alkyl group, specifically, for example: an alkyl group with 1 to 5 carbon atoms (methyl, ethyl, propyl, etc.) , isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl) and the like. In addition, the halogenated alkyl group as the substituent at the α-position, specifically, one in which part or all of the hydrogen atoms of the above-mentioned "alkyl group as the substituent at the α-position" is substituted with a halogen atom can be mentioned. Base etc. The halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is particularly preferable. In addition, specific examples of the hydroxyalkyl group as the substituent at the α-position include groups obtained by substituting a part or all of the hydrogen atoms of the above-mentioned "alkyl group as the substituent at the α-position" with hydroxyl groups. wait. The number of hydroxyl groups in the hydroxyalkyl group is preferably from 1 to 5, and most preferably 1.

In this specification and the patent scope of this application, there may be asymmetric carbons depending on the structure represented by the chemical formula, so there may be enantiomers or diastereomers. The situation is These isomers are represented using one general formula. These isomers may be used alone or as a mixture.

(resist composition) The resist composition of the present embodiment generates acid by exposure, and changes the solubility of the developing solution by the action of the acid. This resist composition contains the substrate component (A) (hereinafter, also referred to as "component (A)") whose solubility in a developer is changed by the action of an acid.

When a resist film is formed using the resist composition of this embodiment and the resist film is selectively exposed, an acid is generated in the exposed portion of the resist film, and (A) While the solubility of the component to the developer changes, but in the unexposed part of the resist film, because the solubility of the component (A) to the developer does not change, the exposed part and the unexposed part of the resist film Differences in solubility to the developer occur between exposed parts. Therefore, when developing the resist film, when the resist composition is positive, the exposed portion of the resist film is dissolved and removed to form a positive resist pattern, and when the resist composition is negative, the resist pattern is formed. The unexposed part of the resist film is dissolved and removed to form a negative resist pattern.

In this specification, the resist composition in which the exposed part of the resist film is dissolved and removed to form a positive resist pattern is called a positive resist composition, and the unexposed part of the resist film is dissolved and removed to form a negative resist. Patterned resist composition is called negative resist composition. The resist composition of this embodiment may be a positive resist composition or a negative resist composition. In addition, the resist composition of this embodiment can be used in an alkaline development process using an alkali developing solution as the developing treatment when forming the resist pattern, and it is also possible to use a developing solution containing an organic solvent (organic solvent) in the developing treatment. The solvent development process of developer solution) is also available. That is, the resist composition of this embodiment is: a "positive resist composition for alkali developing process" that can form a positive resist pattern in an alkali developing process, and can form a negative resist pattern in a solvent developing process Graphical "Negative Resist Composition for Solvent Development Process".

The resist composition of this embodiment has the ability to generate acid by exposure to acid, which can be: (A) component can generate acid by exposure, (A) component and other added additive components can be Those who produce acid due to exposure are also acceptable. Specifically, the resist composition of the embodiment may be: (1) may contain an acid generator component (B) (hereinafter, also referred to as "component (B)") that generates acid upon exposure; 2) Component (A) may be a component that generates acid upon exposure; (3) Component (A) may be a component that generates acid upon exposure, and may also contain component (B). That is, in the case of the above (2) or (3), (A) component is "the base material component which generates acid by exposure and changes the solubility to the developer by the action of an acid." When the component (A) is a substrate component that generates an acid through exposure and changes the solubility of the developer through the action of the acid, the component (A1) described later generates an acid through exposure and, through the action of the acid, generates an acid. The polymer compound that changes the solubility of the developing solution due to the action of the polymer compound is preferred. As these polymer compounds, copolymers having a structural unit that generates acid upon exposure can be used. As a structural unit which generates an acid by exposure, a well-known structural unit etc. are mentioned, for example. The resist composition of this embodiment is particularly preferred in the case of (1) above.

＜(A)Ingredient＞ Component (A) is a substrate component whose solubility in a developer solution changes through the action of an acid. In the present invention, the "substrate component" is an organic compound having film-forming ability, preferably an organic compound with a molecular weight of 500 or more. When the molecular weight of the organic compound is more than 500, the film forming ability can be improved, and in addition, the resist pattern of about nanometer can be easily formed. Organic compounds used as substrate components can be broadly classified into non-polymers and polymers. For non-polymers, those with a molecular weight of 500 or more and less than 4,000 are usually used. Hereinafter, when "low molecular weight compound" is referred to, it means a non-polymer having a molecular weight of 500 or more and less than 4,000. Polymers generally use those with a molecular weight of 1,000 or more. Hereinafter, when referred to as "resin", "high molecular compound" or "polymer", it means a polymer having a molecular weight of 1000 or more. The molecular weight of the polymer is a weight average molecular weight obtained in terms of polystyrene using GPC (gel permeation chromatography).

The component (A) in the resist composition of the present embodiment contains a resin component (A1) whose solubility in a developer is changed by the action of an acid (hereinafter also referred to as "component (A1)"). In (A) component, in order to use at least (A1) component, you may use together with this (A1) component, another high molecular compound and/or a low molecular compound.

≪(A1) Ingredients≫ (A1) A component has a structural unit (a0) represented by general formula (a0) mentioned later. The component (A1) may have other structural units as necessary in addition to the structural unit (a0).

In the resist composition of this embodiment, since the structural unit (a0) contains an acid dissociative group, when the component (A1) is used, the polarity of the resin component before and after exposure will change, so not only in the alkali developing process, Even in the solvent development process, good development contrast can be obtained between the exposed and unexposed portions of the resist film.

When used in the alkali developing process, the (A1) component is insoluble in the alkaline developing solution before exposure. For example, when the acid is generated from the (B) component through exposure, the polarity is increased through the action of the acid, thereby increasing High solubility to alkaline developer. Therefore, when selectively exposing the resist film obtained by coating the resist composition on the support in the formation of the resist pattern, the exposure part of the resist film changes due to the poor solubility of the alkaline developer. While being soluble, the unexposed part of the resist film is still hardly soluble in alkali without any change. When alkali development is performed, a positive resist pattern can be formed. On the other hand, when used in a solvent developing process, the component (A1) has high solubility to the organic developer before exposure, for example, when an acid is generated from the component (B) through exposure, the acid will This increases the polarity, thereby reducing the solubility to organic developer solutions. Therefore, when selectively exposing the resist film obtained by coating the resist composition on the support during the formation of the resist pattern, it is difficult to change the solubility of the exposed part of the resist film to the organic developer. While being soluble, the unexposed part of the resist film is still soluble without any change. When developing with an organic developer, a negative resist pattern can be formed.

Structural unit (a0): The structural unit (a0) is a structural unit represented by the following general formula (a0). The structural unit (a0) contains an acid-decomposable group whose polarity is increased by the action of an acid. "Acid-decomposable group" means an acid-decomposable group in which at least a part of the bonds in the structure of the acid-decomposable group are cleaved by the action of an acid. In ^the structural unit (a0) ^, the oxygen atom (-O- ) to form a bond between cracks, and generate a highly polar polar group (carboxyl group), which increases the polarity.

[式中，R⁰ 為氫原子、碳數1～5之烷基、鹵素原子或碳數1～5之鹵化烷基；Va^x0 為單鍵或2價之連結基；Wa為可具有取代基的2價之芳香族烴基；Va⁰ 為可具有醚鍵結的2價之烴基；n_a0 為0～2之整數；Ra⁰⁰ 為酸解離性基]。

[wherein, R ⁰ is a hydrogen atom, an alkyl group with 1 to 5 carbons, a halogen atom or a halogenated alkyl group with 1 to 5 carbons; Va ^x0 is a single bond or a divalent linking group; Wa is an optional substituent 2-valent aromatic hydrocarbon group; Va ⁰ is a 2-valent hydrocarbon group that may have ether linkage; n _a0 is an integer from 0 to 2; Ra ⁰⁰ is an acid dissociative group].

In the aforementioned formula (a0), R ⁰ is a hydrogen atom, an alkyl group with 1 to 5 carbons, a halogen atom or a halogenated alkyl group with 1 to 5 carbons; the alkyl group with 1 to 5 carbons in R ⁰ is represented by carbon A linear or branched alkyl group with a number of 1 to 5 is preferred, specifically, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert- Butyl, pentyl, isopentyl, neopentyl, etc. The halogen atom in R ⁰ includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred. The halogenated alkyl group having 1 to 5 carbon atoms in R ⁰ is a group obtained by substituting part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms described above with the aforementioned halogen atom. R ⁰ is preferably a hydrogen atom, an alkyl group with 1 to 5 carbons, a fluorine atom, or a fluorinated alkyl group with 1 to 5 carbons. In terms of the ease of industrial acquisition, a hydrogen atom, a methyl group or a fluorine atom is preferred. More preferably, a hydrogen atom is particularly preferred.

In the aforementioned formula (a0), Va ^x0 is a single bond or a divalent linking group; the divalent linking group of Va ^x0 is not particularly limited, and may be a divalent hydrocarbon group that may have a substituent, a heteroatom-containing The divalent linking group etc. are preferable examples.

・Divalent hydrocarbon group which may have a substituent: When Va ^x0 is a divalent hydrocarbon group which may have a substituent, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

・・Aliphatic hydrocarbon group in Va ^x0 The aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and saturated is generally preferred. The aforementioned aliphatic hydrocarbon group includes, for example, a linear or branched aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in its structure, and the like.

・・・Straight-chain or branched aliphatic hydrocarbon group The straight-chain aliphatic hydrocarbon group preferably has 1 to 10 carbons, more preferably 1 to 6 carbons, and preferably 1 to 4 carbons More preferably, the carbon number is 1-3. Straight-chain aliphatic hydrocarbon groups are preferably straight-chain alkylene groups. Specifically, examples include: methylene [-CH ₂ -], ethylene [-(CH ₂ ) ₂ -], Trimethyl[-(CH ₂ ) ₃ -], Tetramethyl[-(CH ₂ ) ₄ -], Pentamethyl[-(CH ₂ ) ₅ -], etc. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbons, more preferably 3 to 6 carbons, more preferably 3 or 4 carbons, most preferably 3 carbons. Branched-chain aliphatic hydrocarbon groups are preferably branched-chain alkylene groups. Specifically, examples include: -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ - etc. ; -CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C( CH ₂ CH ₃ ) ₂ -CH ₂ - and other alkyl ethylene groups; -CH(CH ₃ ) CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ ) CH ₂ - and other alkyl trimethyl groups; -CH (CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ -, alkylene such as tetramethylene, alkylene such as tetramethyl, etc. The alkyl group in the alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

The aforementioned linear or branched aliphatic hydrocarbon group may or may not have a substituent. The substituent includes, for example, a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms substituted by a fluorine atom, a carbonyl group, and the like.

・・・Aliphatic hydrocarbon group containing a ring in the structure The aliphatic hydrocarbon group containing a ring in the structure includes, for example, a cyclic aliphatic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) that may contain a heteroatom-containing substituent in the ring structure, the aforementioned A cyclic aliphatic hydrocarbon group bonded to the end of a straight-chain or branched aliphatic hydrocarbon group, and the aforementioned cyclic aliphatic hydrocarbon group interposed between a straight-chain or branched aliphatic hydrocarbon group The foundation and so on. It is, for example, the same as the linear or branched aliphatic hydrocarbon group described above. The cyclic aliphatic hydrocarbon group preferably has 3-20 carbons, more preferably 3-12 carbons. The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocyclic alkane. The monocyclic alkanes preferably have 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycyclic alkane, and the polycyclic alkane preferably has 7 to 12 carbon atoms. Specifically, examples include: : Adamantane, Norbornane, Isobornane, Tricyclodecane, Tetracyclododecane, etc.

The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, halogenated alkyl groups, hydroxyl groups, and carbonyl groups. The aforementioned alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. The aforementioned alkoxy group as a substituent is preferably an alkoxy group with 1 to 5 carbon atoms, such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert -Butoxy group is preferred, and methoxy group and ethoxy group are more preferred. The aforementioned halogen atom as a substituent includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred. Examples of the aforementioned halogenated alkyl group as a substituent include groups in which a part or all of the hydrogen atoms of the aforementioned alkyl group are substituted with the aforementioned halogen atoms. In the cyclic aliphatic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted by substituents containing heteroatoms. The heteroatom-containing substituent is preferably -O-, -C(=O)-O-, -S-, -S(=O) ₂ -, -S(=O) ₂ -O-.

・・Aromatic hydrocarbon group in Va ^x0 The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and it may be monocyclic or polycyclic. The carbon number of the aromatic ring is preferably 5-30, more preferably 5-20, more preferably 6-15, particularly preferably 6-10. However, the carbon number does not include the carbon number in the substituent. Aromatic rings, specifically, include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocyclic rings in which some of the carbon atoms constituting the aforementioned aromatic hydrocarbon rings are replaced by heteroatoms wait. The hetero atom in the aromatic heterocycle includes, for example, an oxygen atom, a sulfur atom, a nitrogen atom, and the like. The aromatic heterocycle specifically includes, for example, a pyridine ring, a thiophene ring, and the like. Aromatic hydrocarbon groups, specifically, include: groups obtained by removing two hydrogen atoms from the aforementioned aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl or heteroaryl); aromatic groups containing two or more The group obtained by removing 2 hydrogen atoms from the ring aromatic compound (such as biphenyl, fennel, etc.); the group obtained by removing 1 hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle (aryl or heteroaryl ) in which one of the hydrogen atoms is replaced by an alkylene group (for example: benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2 - a group obtained by removing one hydrogen atom from an aryl group in an aralkyl group such as naphthylethyl group), etc. The aforementioned aryl or heteroaryl-bonded alkylene group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

In the aforementioned aromatic hydrocarbon group, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a substituent. For example: the hydrogen atom bonded to the aromatic ring in the aromatic hydrocarbon group may be replaced by a substituent. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, halogenated alkyl groups, and hydroxyl groups. The aforementioned alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. Examples of the alkoxy group, a halogen atom, and a halogenated alkyl group as the substituent include those that are exemplified as substituents for substituting the hydrogen atom contained in the cycloaliphatic hydrocarbon group.

・Divalent linking group containing a heteroatom: When Va ^x0 is a divalent linking group containing a heteroatom, the preferred examples of the linking group include: -O-, -C(=O)-O- , -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H can be substituted by substituents such as alkyl, acyl, etc.), -S-, -S(=O) ₂ -, -S(=O) ₂ -O-, general formula -Y ²¹ -OY ²² - , -Y ²¹ -O-, -Y ²¹ -C(=O)-O-, -C(=O)-OY ²¹ -, -[Y ²¹ -C(=O)-O] _m” -Y ²² -, -Y ²¹ -OC(=O)-Y ²² -or -Y ²¹ -S(=O) ₂ -OY ²² - The group represented by [wherein, Y ²¹ and Y ²² are independently substituted A divalent hydrocarbon group, O is an oxygen atom, m" is an integer from 0 to 3], etc. The aforementioned divalent linking groups containing heteroatoms are -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, -NH-C(=NH)- When , this H may be substituted by a substituent such as an alkyl group or an acyl group. The substituent (alkyl group, acyl group, etc.) preferably has 1-10 carbon atoms, more preferably 1-8 carbon atoms, and particularly preferably 1-5 carbon atoms. General formula -Y ²¹ -OY ²² -, -Y ²¹ -O-, -Y ²¹ -C(=O)-O-, -C(=O)-OY ²¹ -, -[Y ²¹ -C(=O )-O] _m” -Y ²² -, -Y ²¹ -OC(=O)-Y ²² - or -Y ²¹ -S(=O) ₂ -OY ²² -, Y ²¹ and Y ²² are independently A divalent hydrocarbon group which may have a substituent. The divalent hydrocarbon group is, for example, the same as the (divalent hydrocarbon group which may have a substituent) listed when describing the divalent linking group in Ya ^x1 above. Y ²¹ is preferably a straight-chain aliphatic hydrocarbon group, preferably a straight-chain alkylene group, more preferably a straight-chain alkylene group with 1 to 5 carbons, and preferably a straight-chain alkylene group with a carbon number of 1-5. The base is particularly preferred. ^Y22 is preferably a straight-chain or branched aliphatic hydrocarbon group, preferably a methylene group, an ethylidene group or an alkylene group. The alkyl group in the alkylene group is preferably A linear alkyl group with 1 to 5 carbons is preferred, a linear alkyl group with 1 to 3 carbons is preferred, and methyl is the most preferred. Formula -[Y ²¹ -C(=O) -O] _m” -Y ²² - Among the bases represented, m” is an integer of 0 to 3, preferably an integer of 0 to 2, preferably 0 or 1, and particularly preferably 1. That is, The group represented by the formula -[Y ²¹ -C(=O)-O] _m” -Y ²² - is particularly preferably represented by the formula -Y ²¹ -C(=O)-OY ²² -. Among them, the group represented by the formula -(CH ₂ ) _a' -C(=O)-O-(CH ₂ ) _b' - is preferable. In the formula, a' is an integer of 1-10, preferably an integer of 1-8, more preferably an integer of 1-5, more preferably 1 or 2, and most preferably 1. b' is an integer of 1-10, preferably an integer of 1-8, more preferably an integer of 1-5, more preferably 1 or 2, and most preferably 1.

Among the above, Va ^x0 is single bonded, ester bonded [-C(=O)-O-, -OC(=O)-], ether bonded (-O-), linear or branched An alkylene group, or a combination thereof is preferred, a single bond or an ester bond [-C(=O)-O-, -OC(=O)-] is preferred, and a single bond is more preferred.

In the aforementioned formula (a0), Wa is a divalent aromatic hydrocarbon group which may have a substituent; The aromatic hydrocarbon group in Wa includes, for example, a group obtained by removing two hydrogen atoms from an aromatic ring, and the like. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and it may be monocyclic or polycyclic. The carbon number of the aromatic ring is preferably 5-30, more preferably 5-20, more preferably 6-15, particularly preferably 6-10. Specifically, the aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; Ring etc. The hetero atom in the aromatic heterocycle includes, for example, an oxygen atom, a sulfur atom, a nitrogen atom, and the like. The aromatic heterocycle specifically includes, for example, a pyridine ring, a thiophene ring, and the like. In addition, the aromatic hydrocarbon group in Wa also includes, for example, a group obtained by removing two hydrogen atoms from an aromatic compound (such as biphenyl, fennel, etc.) containing two or more aromatic rings. Among the above, Wa is preferably a group obtained by removing 2 hydrogen atoms from benzene, naphthalene, anthracene or biphenyl, and a group obtained by removing 2 hydrogen atoms from benzene or naphthalene (that is, phenylene or phenylene). Naphthyl) is preferable, and a group obtained by removing two hydrogen atoms from benzene (ie, phenylene) is more preferable.

The substituents that the divalent aromatic hydrocarbon group of Wa may have include, for example, straight-chain or branched-chain alkyl groups having 1 to 5 carbon atoms, halogen atoms, and straight-chain or branched-chain alkyl groups having 1 to 5 carbon atoms. Haloalkyl, etc. Straight-chain or branched-chain alkyl groups with 1 to 5 carbons, such as: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, Isopentyl, neopentyl, etc., and methyl is preferred. The halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred. The halogenated alkyl group having 1 to 5 carbons is a group obtained by substituting part or all of the hydrogen atoms of the alkyl group having 1 to 5 carbons with the aforementioned halogen atom.

In the aforementioned formula (a0), Va ^x1 is a divalent hydrocarbon group which may have an ether bond; the divalent hydrocarbon group in Va ^x1 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

The aliphatic hydrocarbon group as the divalent hydrocarbon group in Va ^x1 may be saturated or unsaturated, but usually saturated is preferred. More specifically, the aliphatic hydrocarbon group includes, for example, a linear or branched aliphatic hydrocarbon group, or an aliphatic hydrocarbon group having a ring in its structure, and the like.

The aforementioned linear aliphatic hydrocarbon group preferably has 1-10 carbon atoms, more preferably 1-6 carbon atoms, more preferably 1-4 carbon atoms, most preferably 1-3 carbon atoms. Straight-chain aliphatic hydrocarbon groups are preferably straight-chain alkylene groups. Specifically, examples include: methylene [-CH ₂ -], ethylene [-(CH ₂ ) ₂ -], Trimethyl[-(CH ₂ ) ₃ -], Tetramethyl[-(CH ₂ ) ₄ -], Pentamethyl[-(CH ₂ ) ₅ -], etc. The aforementioned branched aliphatic hydrocarbon group preferably has 2-10 carbon atoms, more preferably 3-6 carbon atoms, more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. Branched-chain aliphatic hydrocarbon groups are preferably branched-chain alkylene groups. Specifically, examples include: -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ -, etc. ; -CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C( CH ₂ CH ₃ ) ₂ -CH ₂ - and other alkyl ethylene groups; -CH(CH ₃ ) CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ ) CH ₂ - and other alkyl trimethyl groups; -CH (CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ -, alkylene such as tetramethyl, alkylene such as tetramethyl, etc. The alkyl group in the alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

Examples of aliphatic hydrocarbon groups containing rings in the aforementioned structure include: alicyclic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), alicyclic hydrocarbon groups bonded to straight or branched chains A group obtained at the end of an aliphatic hydrocarbon group, a group obtained by interposing an alicyclic hydrocarbon group in the middle of a linear or branched aliphatic hydrocarbon group, etc. The aforementioned straight-chain or branched aliphatic hydrocarbon group is, for example, the same as the aforementioned straight-chain aliphatic hydrocarbon group or the aforementioned branched-chain aliphatic hydrocarbon group. The aforementioned alicyclic hydrocarbon group preferably has 3-20 carbon atoms, more preferably 3-12 carbon atoms. The aforementioned alicyclic hydrocarbon group may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocyclic alkane. The monocyclic alkane preferably has 3 to 6 carbon atoms, specifically, cyclopentane, cyclohexane, etc. can be mentioned. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycyclic alkane, and the polycyclic alkane preferably has 7 to 12 carbon atoms. Specifically, examples include: Adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

The aromatic hydrocarbon group which is a divalent hydrocarbon group in Va ^x1 is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3-30 carbon atoms, more preferably 5-30 carbon atoms, more preferably 5-20 carbon atoms, particularly preferably 6-15 carbon atoms, most preferably 6-10 carbon atoms. However, the carbon number does not include the carbon number in the substituent. Aromatic rings possessed by aromatic hydrocarbon groups, specifically, aromatic hydrocarbon rings such as benzene, biphenyl, fennel, naphthalene, anthracene, phenanthrene, etc.; a part of the carbon atoms constituting the aforementioned aromatic hydrocarbon rings Aromatic heterocycles substituted by heteroatoms, etc. The hetero atom in the aromatic heterocycle includes, for example, an oxygen atom, a sulfur atom, a nitrogen atom, and the like. The aromatic hydrocarbon group specifically includes, for example: a group obtained by removing two hydrogen atoms from the above-mentioned aromatic hydrocarbon ring (arylene group); a group obtained by removing one hydrogen atom from the above-mentioned aromatic hydrocarbon ring ( Aryl) in which one of the hydrogen atoms is replaced by an alkylene group (for example: benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl , 2-naphthylethyl and other aralkyl groups obtained by removing one hydrogen atom from the aryl group) and the like. The number of carbon atoms in the aforementioned alkylene group (the alkyl chain in the aralkyl group) is preferably 1-4, more preferably 1-2, and particularly preferably 1.

In the aforementioned formula (a0), n _a0 is an integer of 0 to 2, preferably 0 or 1, more preferably 0.

In the aforementioned formula (a0), Ra ⁰⁰ is an acid dissociative group; the "acid dissociative group" here refers to: (i) through the action of an acid, the acid dissociative group is adjacent to the acid dissociative group Acid-dissociable groups that form bonds between atoms, or (ii) part of the bonds are formed by the action of an acid, and then the acid-dissociable groups are made Bonds between atoms adjacent to the acid-dissociative group form the cleavage group, and so on. The acid-dissociable group constituting the acid-dissociable group must have a lower polarity than the polar group formed by dissociation of the acid-dissociable group. A polar group having a higher polarity than the acid dissociative group is generated to increase the polarity. As a result, the polarity of the (A1) component will increase as a whole. As a result of the increase in polarity, the solubility to the developer is relatively changed. When the developer is an alkaline developer, the solubility will be increased, and when the developer is an organic developer, the solubility will be reduced.

The acid dissociative group of Ra ⁰⁰ , for example, can be used as the acid dissociative group of the base resin proposed so far as the chemically amplified resist composition. Those proposed as the acid-dissociative group of the base resin for the chemically amplified resist composition specifically include the "acetal-type acid-dissociative group" and "tertiary alkyl ester-type acid-dissociative groups" described below. Sexual group", "tertiary alkoxycarbonyl acid dissociative group, etc.

・Acetal type acid dissociative group: Among the aforementioned polar groups, the acid-dissociating groups that protect carboxyl or hydroxyl groups include, for example, acid-dissociating groups represented by the following general formula (a1-r-1) (hereinafter also referred to as "acetal-type acid-dissociating groups"). Base") and so on.

[式中，Ra’¹ 、Ra’² 為氫原子或烷基；Ra’³ 為烴基，且Ra’³ 可與Ra’¹ 、Ra’² 之任一者鍵結而形成環]。

[wherein, Ra' ¹ and Ra' ² are hydrogen atoms or alkyl groups; Ra' ³ is a hydrocarbon group, and Ra' ³ can be bonded with any of Ra' ¹ and Ra' ² to form a ring].

In the formula (a1-r-1), it is preferable that at least one of ^Ra'1 and ^Ra'2 is a hydrogen atom, and it is more preferable that both are hydrogen atoms. When ^Ra'1 or ^Ra'2 is an alkyl group, the alkyl group is, for example, the same as the alkyl group listed as a substituent that can be bonded to a carbon atom at the α-position in the description of the above-mentioned α-substituted acrylate, and An alkyl group having 1 to 5 carbon atoms is preferred. Specifically, a linear or branched alkyl group is preferably exemplified. More specifically, examples include: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. Methyl or ethyl is preferred, and methyl is particularly preferred.

In the formula (a1-r-1), the hydrocarbon group of ^Ra'3 includes, for example, straight-chain or branched-chain alkyl groups, cyclic hydrocarbon groups, and the like. The linear alkyl group preferably has 1-5 carbon atoms, more preferably 1-4 carbon atoms, more preferably 1 or 2 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group etc. are mentioned. Among these, methyl, ethyl or n-butyl is preferable, and methyl or ethyl is more preferable.

The branched alkyl group preferably has 3-10 carbon atoms, more preferably 3-5 carbon atoms. Specifically, examples include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, 2,2-dimethylbutyl, etc. Also, isopropyl is preferred.

When ^Ra'3 is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a polycyclic group or a monocyclic group. The monocyclic aliphatic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from a monocyclic alkane. The monocyclic alkanes preferably have 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The aliphatic hydrocarbon group of the polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycyclic alkane, and the polycyclic alkane preferably has 7 to 12 carbon atoms. Specifically, examples include: : Adamantane, Norbornane, Isobornane, Tricyclodecane, Tetracyclododecane, etc.

When the cyclic hydrocarbon group of ^Ra'3 is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and it may be monocyclic or polycyclic. The carbon number of the aromatic ring is preferably 5-30, more preferably 5-20, more preferably 6-15, and particularly preferably 6-10. Aromatic rings, specifically, include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocyclic rings in which some of the carbon atoms constituting the aforementioned aromatic hydrocarbon rings are replaced by heteroatoms wait. The hetero atom in the aromatic heterocycle includes, for example, an oxygen atom, a sulfur atom, a nitrogen atom, and the like. The aromatic heterocycle specifically includes, for example, a pyridine ring, a thiophene ring, a furan ring, and the like. The aromatic hydrocarbon group in Ra' ³ , specifically, can be enumerated such as: the base (aryl or heteroaryl) obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocyclic ring; A group obtained by removing one hydrogen atom from the above-mentioned aromatic compound (such as biphenyl, fennel, etc.); one of the hydrogen atoms of the above-mentioned aromatic hydrocarbon ring or aromatic heterocycle is replaced by an alkylene group (Aralkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.) etc. can be mentioned. The number of carbon atoms in the alkylene group bonded to the aforementioned aromatic hydrocarbon ring or aromatic heterocyclic ring is preferably 1-4, more preferably 1-2, and particularly preferably 1.

When Ra' ³ is bonded to any one of Ra' ¹ and Ra' ² to form a ring, the cyclic group is preferably a 4-7-membered ring, more preferably a 4-6-membered ring. Specific examples of the cyclic group include, for example, tetrahydropyranyl, tetrahydrofuranyl, and the like.

In the formula (a1-r-1), the hydrocarbon group of ^Ra'3 is preferably a cyclic aliphatic hydrocarbon group, preferably a polycyclic aliphatic hydrocarbon group, such as adamantane, norbornane, isocamphene A group obtained by removing one hydrogen atom from alkane, tricyclodecane or tetracyclododecane is more preferable, and a group obtained by removing one hydrogen atom from adamantane is particularly preferable.

・Tertiary alkyl ester type acid dissociative group: Among the above-mentioned polar groups, the acid-dissociable group protecting the carboxyl group includes, for example, an acid-dissociable group represented by the following general formula (a1-r-2). Also, among the acid-dissociating groups represented by the following formula (a1-r-2), those composed of alkyl groups are also referred to as "tertiary alkyl ester-type acid-dissociating groups" hereinafter for convenience.

[式中，Ra’⁴ ～Ra’⁶ 各別獨立為可具有取代基之烴基，且Ra’⁵ 、Ra’⁶ 可相互鍵結而形成環]。

[In the formula, Ra' ⁴ to Ra' ⁶ are each independently a hydrocarbon group which may have a substituent, and Ra' ⁵ and Ra' ⁶ may be bonded to each other to form a ring].

The hydrocarbon groups that may have substituents for Ra' ⁴ to Ra' ⁶ include, for example, straight-chain or branched-chain alkyl groups (chain-like alkyl groups), straight-chain or branched-chain alkenyl groups (chain-like alkenyl), or cyclic hydrocarbon groups, etc.

The linear alkyl group of Ra' ⁴ to Ra' ⁶ preferably has 1-20 carbons, more preferably 1-15 carbons, most preferably 1-10 carbons. Specifically, examples include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl base, isotridecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, two Undecyl, behenyl, etc.

The branched chain alkyl group of ^Ra'4 - ^Ra'6 preferably has 3-20 carbon atoms, more preferably 3-15 carbon atoms, most preferably 3-10 carbon atoms. Specifically, examples include: 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, etc.

The linear or branched alkenyl groups of Ra' ⁴ to Ra' ⁶ preferably have 2-10 carbon atoms, more preferably 2-5 carbon atoms, more preferably 2-4 carbon atoms, and particularly preferably 3 carbon atoms. Straight-chain alkenyl, such as vinyl, propenyl (allyl), butynyl, etc. Branched alkenyl, for example: 1-methacryl, 2-methacryl, etc.

The chained alkyl group or chained alkenyl group of Ra' ⁴ to Ra' ⁶ may have a substituent. The chained alkyl or chained alkenyl of Ra' ⁴ to Ra' ⁶ may have substituents, for example: hydroxyl group, ether bond (-O-), etc.

The cyclic hydrocarbon groups of Ra' ⁴ to Ra' ⁶ may be polycyclic or monocyclic. In addition, the cyclic hydrocarbon group of Ra' ⁴ to Ra' ⁶ may be an alicyclic hydrocarbon group, or a condensed ring group obtained by condensing an aromatic ring on an alicyclic hydrocarbon group. The monocyclic aliphatic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from a monocyclic alkane or a monocyclic olefin. The monocyclic alkanes preferably have 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The monocyclic olefin preferably has 3 to 6 carbon atoms, and specific examples include cyclopentene and cyclohexene. The polycyclic aliphatic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from polycyclic alkanes or polycyclic alkenes. The polycyclic alkanes preferably have 7 to 12 carbon atoms, specifically , for example, adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like. In addition, the polycyclic olefin preferably has 7 to 12 carbon atoms, and specifically, adamantene, norcamphene, isocamphene, tricyclodecene, tetracyclododecene, and the like can be exemplified. Condensed cyclic groups obtained by condensing an aromatic ring on an alicyclic hydrocarbon group include, for example, groups obtained by removing one hydrogen atom from the aliphatic ring of bicyclic compounds such as tetralin and indanes, etc. . In the cyclic aliphatic hydrocarbon groups of Ra' ⁴ to Ra' ⁶ , some of the carbon atoms constituting the ring structure may be substituted by substituents containing heteroatoms. The heteroatom-containing substituent is preferably -O-, -C(=O)-O-, -S-, -S(=O) ₂ -, -S(=O) ₂ -O-.

The aromatic hydrocarbon groups of Ra' ⁴ to Ra' ⁶ are hydrocarbon groups having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbons, more preferably 5 to 30 carbons, more preferably 5 to 20 carbons, particularly preferably 6 to 15 carbons, and 6 to 10 carbons. for the best. However, the carbon number does not include the carbon number in the substituent. The aromatic ring possessed by the aromatic hydrocarbon group in R ¹⁰¹ specifically includes: benzene, stilbene, naphthalene, anthracene, phenanthrene, biphenyl, or some of the carbon atoms constituting these aromatic rings are replaced by heteroatoms Aromatic heterocycles obtained by substitution, etc. The hetero atom in the aromatic heterocycle includes, for example, an oxygen atom, a sulfur atom, a nitrogen atom, and the like. The aromatic heterocycle specifically includes, for example, a thiophene ring, a furan ring, a pyridine ring, and the like. The aromatic hydrocarbon group in R ¹⁰¹ specifically includes, for example, a group obtained by removing one hydrogen atom from the aforementioned aromatic ring (aryl: such as phenyl, naphthyl, etc.), one of the hydrogen atoms of the aforementioned aromatic ring A group substituted by an alkylene group (such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.) alkyl, etc.) etc. The carbon number of the aforementioned alkylene group (alkane chain in the aralkyl group) is preferably 1-4, more preferably 1-2, and particularly preferably 1.

The cyclic hydrocarbon groups of Ra' ⁴ to Ra' ⁶ may have substituents. The substituents that the cyclic hydrocarbon groups of Ra' ⁴ to Ra' ⁶ may have include, for example: halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), -R ^P1 , -R ^P2 -OR ^P1 , - R ^P2 -CO-R ^P1 , -R ^P2 -CO-OR ^P1 , -R ^P2 -O-CO-R ^P1 , -R ^P2 -OH, -R ^P2 -CN or -R ^P2 -COOH (hereinafter, these The substituents are collectively referred to as “Ra ⁰⁶ ”) and the like. Among them, R ^P1 is a monovalent chain saturated hydrocarbon group having 1 to 10 carbons, a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbons, or a monovalent aromatic hydrocarbon group having 6 to 30 carbons. Also, R ^P2 is a single bond, a divalent chain saturated hydrocarbon group having 1 to 10 carbons, a divalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbons, or a divalent aromatic hydrocarbon group having 6 to 30 carbons . Among them, some or all of the hydrogen atoms in the chain saturated hydrocarbon groups, aliphatic cyclic saturated hydrocarbon groups and aromatic hydrocarbon groups of R ^P1 and R ^P2 may be substituted by fluorine atoms. The above-mentioned aliphatic cyclic hydrocarbon group may have one or more of the above-mentioned substituents alone, or may have one or more of plural kinds of the above-mentioned substituents. Examples of monovalent chain saturated hydrocarbon groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl. Monovalent aliphatic cyclic saturated hydrocarbon groups with 3 to 20 carbons, examples include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl Monocyclic aliphatic saturated ^hydrocarbon groups such as alkyl ^; 6.2.1.1 ^3,6 .0 ^2,7 ] Polycyclic aliphatic saturated hydrocarbon groups such as dodecyl, adamantyl, etc. Examples of monovalent aromatic hydrocarbon groups having 6 to 30 carbon atoms include groups obtained by removing one hydrogen atom from aromatic hydrocarbon rings such as benzene, biphenyl, fennel, naphthalene, anthracene, and phenanthrene.

In the aforementioned formula (a1-r-2), when ^Ra'5 and ^Ra'6 are bonded to each other to form a ring, the group represented by the following general formula (a1-r2-1), the following general formula (a1-r2 The group represented by -2) and the group represented by the following general formula (a1-r2-3) are preferable examples. On the other hand, in the aforementioned formula (a1-r-2), when Ra' ⁴ to Ra' ⁶ are not bonded to each other but are independent hydrocarbon groups, the group represented by the following general formula (a1-r2-4) is better example.

[式(a1-r2-1)中，Ra’¹⁰ 為碳數1～10之烷基，Ra’¹¹ 表示可與Ra’¹⁰ 鍵結的碳原子共同於脂環式烴基或脂環式烴基上縮合芳香族環而形成縮合環式基之基。式(a1-r2-2)中，Ya為碳原子；Xa為與Ya共同形成環狀烴基之基；該環狀之烴基所具有的氫原子之一部份或全部可被取代。Ra⁰¹ ～Ra⁰³ 各別獨立為氫原子、碳數1～10的1價之鏈狀飽和烴基或碳數3～20的1價之脂肪族環狀飽和烴基。該鏈狀飽和烴基及脂肪族環狀飽和烴基所具有的氫原子之一部份或全部可被取代。Ra⁰¹ ～Ra⁰³ 之2個以上可相互鍵結而形成環狀結構。＊表示鍵結鍵。式(a1-r2-3)中，Yaa為碳原子；Xaa為與Yaa共同形成脂肪族環式基之基。Ra⁰⁴ 為可具有取代基的芳香族烴基。 ＊表示鍵結鍵。式(a1-r2-4)中，Ra’¹² 及Ra’¹³ 各別獨立為碳數1～10的1價之鏈狀飽和烴基或氫原子。該鏈狀飽和烴基所具有的氫原子之一部份或全部可被取代。Ra’¹⁴ 為可具有取代基的芳香族烴基。＊表示鍵結鍵(以下相同)]。

[In the formula (a1-r2-1), Ra' ¹⁰ is an alkyl group with 1 to 10 carbon atoms, and Ra' ¹¹ means that the carbon atom that can be bonded to Ra' ¹⁰ is jointly on the alicyclic hydrocarbon group or the alicyclic hydrocarbon group A group that condenses an aromatic ring to form a condensed ring group. In the formula (a1-r2-2), Ya is a carbon atom; Xa is a group forming a cyclic hydrocarbon group together with Ya; a part or all of the hydrogen atoms of the cyclic hydrocarbon group can be substituted. Ra ⁰¹ to Ra ⁰³ are each independently a hydrogen atom, a monovalent chain saturated hydrocarbon group having 1 to 10 carbons, or a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbons. Part or all of the hydrogen atoms of the chain saturated hydrocarbon group and the aliphatic cyclic saturated hydrocarbon group may be substituted. Two or more of Ra ⁰¹ to Ra ⁰³ may be bonded to each other to form a ring structure. ＊Indicates a bonding key. In the formula (a1-r2-3), Yaa is a carbon atom; Xaa is a group forming an aliphatic ring group together with Yaa. Ra ⁰⁴ is an aromatic hydrocarbon group which may have a substituent. ＊Indicates a bonding key. In the formula (a1-r2-4), ^Ra'12 and ^Ra'13 are each independently a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. Part or all of the hydrogen atoms of the chain saturated hydrocarbon group may be substituted. ^Ra'14 is an aromatic hydrocarbon group which may have a substituent. ＊ means a bonding key (the same below)].

In formula (a1-r2-1), the alkyl group with 1 to ¹⁰ carbon atoms in Ra'10 is listed as the linear or branched alkyl group in ^Ra'3 in formula (a1-r-1). The foundation is good. ^Ra'10 is preferably an alkyl group having 1 to 5 carbon atoms. In the formula (a1-r2-1), the condensed ring-type group obtained by condensing an aromatic ring on the aliphatic ring-type group or the alicyclic-type hydrocarbon group formed by the carbon atom bonded by Ra' ¹¹ and Ra' ¹⁰ is represented by the formula The cyclic hydrocarbon groups of Ra' ⁴ to Ra' ⁶ in (a1-r-2) are preferably the groups listed, and the groups obtained by removing one hydrogen atom from monocyclic alkanes or polycyclic alkanes are preferred Preferably, the group obtained by removing one hydrogen atom from cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane is more preferred, and the group obtained from cyclopentane A group obtained by removing one hydrogen atom from alkane or adamantane is particularly preferred. In the aliphatic ring group formed by the carbon atoms bonded by ^Ra'11 and ^Ra'10 , a part of the carbon atoms constituting the ring structure can be replaced by a substituent containing a heteroatom. The heteroatom-containing substituent is preferably -O-, -C(=O)-O-, -S-, -S(=O) ₂ -, -S(=O) ₂ -O-.

In the formula (a1-r2-2), Xa and Ya together form a cyclic hydrocarbon group, preferably the groups listed as the cyclic hydrocarbon groups of Ra' ⁴ ~ Ra' ⁶ in the aforementioned formula (a1-r-2) , the group obtained by removing one hydrogen atom from monocyclic alkane is preferred, the group obtained by removing one hydrogen atom from cyclopentane or cyclohexane is preferred, and the group obtained by removing one hydrogen atom from cyclopentane The base derived from a hydrogen atom is more preferred. Xa and Ya together form a cyclic hydrocarbon group, which may have a substituent. Examples of the substituents include the same substituents as the cyclic hydrocarbon groups of Ra' ⁴ to Ra' ⁶ in the formula (a1-r-2). In the formula (a1-r2-2), among Ra ⁰¹ to Ra ⁰³ , monovalent chained saturated hydrocarbon groups with 1 to 10 carbons include, for example: methyl, ethyl, propyl, butyl, pentyl, Hexyl, heptyl, octyl, decyl, etc. Among Ra ⁰¹ to Ra ⁰³ , monovalent aliphatic cyclic saturated hydrocarbon groups with 3 to 20 carbons include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, Monocyclic aliphatic saturated hydrocarbon groups such as cyclodecyl and cyclododecyl; bicyclo[2.2.2]heptyl, tricyclo[5.2.1.0 ^2,6 ]decyl, tricyclo[3.3.1.1 ^3,7 ]decyl, polycyclic aliphatic saturated hydrocarbon groups such as tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodecyl, adamantyl, and the like. Among Ra ⁰¹ to Ra ⁰³ , from the viewpoint of easy synthesis of monomeric compounds derived from the structural unit (a0), hydrogen atoms and monovalent chain-like saturated hydrocarbon groups with 1 to 10 carbons are preferred, and among them, hydrogen Atoms, methyl groups, and ethyl groups are preferred, and hydrogen atoms are particularly preferred.

Examples of the substituents of the chain saturated hydrocarbon groups represented by Ra ⁰¹ to Ra ⁰³ or the aliphatic cyclic saturated hydrocarbon groups include the same groups as Ra ⁰⁵ above.

Two or more of Ra ⁰¹ to Ra ⁰³ are bonded to each other to form a cyclic structure containing a carbon-carbon double bond. For example: cyclopentenyl, cyclohexenyl, methylcyclopentenyl, Methylcyclohexenyl, cyclopentylenevinyl, cyclohexylenevinyl, etc. Among these, cyclopentenyl, cyclohexenyl, and cyclopentylidenevinyl are preferable from the viewpoint of easy synthesis of monomeric compounds from which the structural unit (a1) is derived.

In formula (a1-r2-3), the aliphatic cyclic group formed by Xaa and Yaa is preferably the group listed as the cyclic hydrocarbon group of Ra' ⁴ ~ Ra' ⁶ in formula (a1-r-2) , preferably a group obtained by removing one hydrogen atom from monocyclic alkane, and preferably a group obtained by removing one hydrogen atom from cyclopentane or cyclohexane. In the formula (a1-r2-3), the aromatic hydrocarbon group in Ra ⁰⁴ includes, for example, a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 5 to 30 carbon atoms. Among them, Ra ⁰⁴ is preferably a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring with 6 to 15 carbon atoms, such as removing one or more hydrogen atoms from benzene, naphthalene, anthracene, phenanthrene, thiophene or furan The group obtained by removing one or more hydrogen atoms from benzene, naphthalene or anthracene is more preferable, and the group obtained by removing one or more hydrogen atoms from benzene or naphthalene is particularly preferable. , the most preferred is the base obtained by removing one or more hydrogen atoms from benzene.

The substituents that Ra ⁰⁴ in the formula (a1-r2-3) may have include, for example: methyl, ethyl, propyl, hydroxyl, carboxyl, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.), alkane Oxygen (methoxy, ethoxy, propoxy, butoxy, etc.), alkyloxycarbonyl, etc.

In the formula (a1-r2-4), ^Ra'12 and ^Ra'13 are each independently a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. In Ra' ¹² and Ra' ¹³ , the monovalent chain saturated hydrocarbon groups having 1 to 10 carbons are, for example, the same as the monovalent chain saturated hydrocarbon groups having 1 to 10 carbons in Ra ⁰¹ to Ra ⁰³ above. same content etc. Part or all of the hydrogen atoms of the chain saturated hydrocarbon group may be substituted. In Ra' ¹² and Ra' ¹³ , a hydrogen atom and an alkyl group with 1 to 5 carbons are preferred, an alkyl group with 1 to 5 carbons is preferred, a methyl group and an ethyl group are more preferred, and a methyl group is preferred. The base is excellent. When the chain-like saturated hydrocarbon group represented by ^Ra'12 and ^Ra'13 above is substituted, the substituent includes, for example, the same group as ^Ra'05 above.

In the formula (a1-r2-4), ^Ra'14 is an aromatic hydrocarbon group which may have a substituent. The aromatic hydrocarbon group in ^Ra'14 includes, for example, the same contents as the aromatic hydrocarbon group in ^Ra04 . Among them, Ra' ¹⁴ is preferably a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring with 6 to 15 carbon atoms, and is obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene or phenanthrene The group obtained by removing one or more hydrogen atoms from benzene, naphthalene or anthracene is more preferred, the group obtained by removing one or more hydrogen atoms from naphthalene or anthracene is particularly preferred, and the group obtained by removing one or more hydrogen atoms from naphthalene or anthracene is particularly preferred. The group obtained by removing one or more hydrogen atoms is most preferable. The substituent that ^Ra'14 may have includes, for example, the same content as the substituent that ^Ra'04 may have.

When ^Ra'14 in the formula (a1-r2-4) is a naphthyl group, its bonding position with the tertiary carbon atom in the aforementioned formula (a1-r2-4) can be the 1 or 2 position of the naphthyl group Either will do. When Ra' ¹⁴ in the formula (a1-r2-4) is an anthracenyl group, its bonding position with the tertiary carbon atom in the aforementioned formula (a1-r2-4) can be the 1-position or 2-position of the anthracenyl group Or any one of 9 digits is acceptable.

Specific examples of the group represented by the aforementioned formula (a1-r2-1) are as follows.

Specific examples of the group represented by the aforementioned formula (a1-r2-2) are as follows.

Specific examples of the group represented by the aforementioned formula (a1-r2-3) are as follows.

Specific examples of the group represented by the aforementioned formula (a1-r2-4) are as follows.

Tertiary alkyloxycarbonyl acid dissociative group: The acid-dissociative groups protecting the hydroxyl groups in the polar groups include, for example, the acid-dissociative groups represented by the following general formula (a1-r-3) (hereinafter, also referred to as "tertiary alkyl groups" for convenience) Oxycarbonyl acid dissociating group").

[式中，Ra’⁷ ～Ra’⁹ 各別為烷基]。

[wherein, Ra' ⁷ to Ra' ⁹ are each an alkyl group].

In the formula (a1-r-3), each of Ra' ⁷ to Ra' ⁹ is preferably an alkyl group having 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. Moreover, the total carbon number of each alkyl group is preferably 3-7, more preferably 3-5, and most preferably 3-4.

In the aforementioned formula (a0), the acid dissociative group of Ra ⁰⁰ is preferably represented by any one of the aforementioned formulas (a1-r2-1) to (a1-r2-4), and the aforementioned formula (a1- The group represented by any one of r2-1) to (a1-r2-3) is preferable.

Specific examples of the structural unit (a0) are described below. In the formula, R ⁰ has the same content as above.

(A1) The structural unit (a0) which a component has may be 1 type or 2 or more types. The proportion of the structural unit (a0) in the component (A1) relative to the total (100 mol%) of all structural units constituting the component (A1) is preferably 30-75 mol%, and 35-70 mol% % is better, more preferably 40-65 mol%. When the proportion of the structural unit (a0) is more than the lower limit value, the lithographic etching characteristics such as sensitivity, resolution, and roughness can be improved. Also, when it is below the upper limit, a balance with other structural units can be achieved.

Other structural units: The component (A1) may have other structural units, if necessary, in addition to the structural unit (a0). Other structural units include, for example: structural unit (a10) represented by the general formula (a10-1); Structural unit (a0 except those); Structural unit (a2) containing cyclic group containing lactone, cyclic group containing -SO ₂ - or cyclic group containing carbonate; aliphatic hydrocarbon group containing polar group Structural units (a3) (except those corresponding to structural units (a1) or structural units (a2)); structural units (a4) containing non-acid dissociative aliphatic ring groups; styrene or its derivatives Structural units derived from substances, etc.

Structural unit (a10): The structural unit (a10) is a structural unit represented by the following general formula (a10-1).

[式中，R為氫原子、碳數1～5之烷基或碳數1～5之鹵化烷基；Ya^x1 為單鍵或2價之連結基。Wa^x1 為(n_ax1 +1)價之芳香族烴基。n_ax1 為1以上之整數]。

[In the formula, R is a hydrogen atom, an alkyl group with 1 to 5 carbons, or a halogenated alkyl group with 1 to 5 carbons; Ya ^x1 is a single bond or a divalent linking group. Wa ^x1 is an aromatic hydrocarbon group with a valence of (n _ax1 +1). n _ax1 is an integer greater than or equal to 1].

In the aforementioned formula (a10-1), R is a hydrogen atom, an alkyl group with 1 to 5 carbons, or a halogenated alkyl group with 1 to 5 carbons; The alkyl group with 1 to 5 carbons in R is preferably a linear or branched chain with 1 to 5 carbons, specifically, methyl, ethyl, propyl, iso Propyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. The halogenated alkyl group having 1 to 5 carbons in R is a group obtained by substituting part or all of the hydrogen atoms of the aforementioned alkyl group having 1 to 5 carbons with halogen atoms. The halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is particularly preferable. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbons, or a fluorinated alkyl group having 1 to 5 carbons, and is preferably a hydrogen atom, a methyl group or a trifluoromethyl group in view of the ease of industrial acquisition. A hydrogen atom or a methyl group is more preferable, and a hydrogen atom is particularly preferable.

In the aforementioned formula (a10-1), Ya ^x1 is a single bond or a divalent linking group. In the aforementioned formula (a10-1), the divalent linking group in Ya ^x1 is, for example, the same as the divalent linking group in Va ^x1 in the aforementioned formula (a0). Among them, Ya ^x1 is extended by single bond, ester bond [-C(=O)-O-, -OC(=O)-], ether bond (-O-), straight chain or branched chain An alkyl group or a combination thereof is preferred, and a single bond or an ester bond [-C(=O)-O-, -OC(=O)-] is preferred.

In the aforementioned formula (a10-1), Wa ^x1 is an aromatic hydrocarbon group having a valence of (n _ax1 +1). The aromatic hydrocarbon group in Wa ^x1 includes, for example, a group obtained by removing (n _ax1 +1) hydrogen atoms from an aromatic ring, and the like. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and it may be monocyclic or polycyclic. The carbon number of the aromatic ring is preferably 5-30, more preferably 5-20, more preferably 6-15, particularly preferably 6-10. Specifically, the aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; Ring etc. The hetero atom in the aromatic heterocycle includes, for example, an oxygen atom, a sulfur atom, a nitrogen atom, and the like. The aromatic heterocycle specifically includes, for example, a pyridine ring, a thiophene ring, and the like. Also, the aromatic hydrocarbon group in Wa ^x1 includes, for example, a group obtained by removing (n _ax1 + 1) hydrogen atoms from an aromatic compound (such as biphenyl, fennel, etc.) containing two or more aromatic rings. . Among the above, Wa ^x1 is preferably a group obtained by removing (n _ax1 +1) hydrogen atoms from benzene, naphthalene, anthracene or biphenyl, and a group obtained by removing (n _ax1 +1) hydrogen atoms from benzene or naphthalene. The base obtained is preferred, and the base obtained by removing (n _ax1 +1) hydrogen atoms from benzene is more preferred.

In the aforementioned formula (a10-1), n _ax1 is an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, more preferably 1, 2 or 3, and preferably 1 or 2 is the best.

The following are specific examples of the structural unit (a10) represented by the aforementioned formula (a10-1). In the following formulae, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

(A1) The structural unit (a10) which a component has may be 1 type, or 2 or more types may be sufficient. When the component (A1) has a structural unit (a10), the ratio of the structural unit (a10) in the component (A1) to the total (100 mol%) of all structural units constituting the component (A1) is 15 to 70 Mole% is preferred, more preferably 20-60 mol%, more preferably 25-55 mol%. When the proportion of the structural unit (a10) is above the lower limit, the sensitivity can be improved more easily. On the other hand, when it is below the upper limit, the balance with other structural units can be easily obtained.

Structural unit (a1): Structural unit (a1) is a structural unit containing an acid-decomposable group whose polarity is increased by the action of acid (excluding those corresponding to structural unit (a0)). The acid-decomposable group whose polarity is increased by the action of an acid includes, for example, a group that is decomposed by the action of an acid to form a polar group. Polar groups include, for example, carboxyl groups, hydroxyl groups, amino groups, sulfonic acid groups (—SO ₃ H) and the like. Among them, a polar group containing -OH in the structure (hereinafter also referred to as "OH-containing polar group") is preferable, a carboxyl group or a hydroxyl group is preferable, and a carboxyl group is particularly preferable. Specific examples of the acid-decomposable group include groups in which the aforementioned polar group is protected by an acid-dissociative group (for example, a hydrogen atom of a polar group containing OH, a group protected by an acid-dissociative group), and the like. The "acid dissociative group" here refers to: (i) through the action of an acid, the bond between the acid dissociative group and the adjacent atoms of the acid dissociative group is formed to form an acid dissociative group , or (ii) after a part of the bond is cleaved by the action of an acid, the bond between the acid dissociative group and the adjacent atom of the acid dissociative group is formed through the resulting decarboxylation reaction The foundation of cracking, and so on. The acid-dissociable group constituting the acid-dissociable group must have a lower polarity than the polar group formed by dissociation of the acid-dissociable group. A polar group having a higher polarity than the acid dissociative group is generated to increase the polarity. As a result, the polarity of the (A1) component will increase as a whole. As a result of the increase in polarity, the solubility to the developer is relatively changed. When the developer is an alkaline developer, the solubility will be increased, and when the developer is an organic developer, the solubility will be reduced.

As the acid dissociative group, for example, the acid dissociative group proposed as the base resin for the chemically amplified resist composition can be used. Those proposed as the acid dissociative group of the base resin ^for the chemically amplified resist composition, specifically, for example: the "acetal type acid dissociation Sexual group", "tertiary alkyl ester type acid dissociative group", "tertiary alkyloxycarbonyl acid dissociative group" and so on.

Structural units (a1) include, for example, structural units derived from acrylic esters, structural units derived from acrylamide, hydroxystyrene or Structural units derived from hydroxystyrene derivatives in which at least a part of the hydrogen atoms in the hydroxyl groups are protected by substituents containing the aforementioned acid-decomposable groups, structural units derived from ethylene benzoic acid or ethylene benzoic acid derivatives A structural unit in which at least a part of the hydrogen atoms in -C(=O)-OH of the structural unit is protected by a substituent containing the aforementioned acid-decomposable group, etc.

Among the above, the structural unit (a1) is preferably a structural unit derived from an acrylate in which a hydrogen atom bonded to a carbon atom at the α position can be replaced by a substituent. Preferable specific examples of the structural unit (a1) include, for example, structural units represented by the following general formula (a1-1) or (a1-2).

[式中，R為氫原子、碳數1～5之烷基或碳數1～5之鹵化烷基；Va¹ 為可具有醚鍵結的2價之烴基；n_a1 為0～2之整數；Ra¹ 為上述通式(a1-r-1)或(a1-r-2)所表示之酸解離性基。Wa¹ 為n_a2 +1價之烴基，n_a2 為1～3之整數，Ra² 為上述式(a1-r-1)或(a1-r-3)所表示之酸解離性基]。

[wherein, R is a hydrogen atom, an alkyl group with 1 to 5 carbons, or a halogenated alkyl group with 1 to 5 carbons; Va ¹ is a divalent hydrocarbon group that may have an ether bond; n _a1 is an integer of 0 to 2 ; Ra ¹ is an acid dissociative group represented by the above general formula (a1-r-1) or (a1-r-2). Wa ¹ is n _a2 + 1-valent hydrocarbon group, n _a2 is an integer of 1 to 3, and Ra ² is an acid dissociative group represented by the above formula (a1-r-1) or (a1-r-3)].

In the aforementioned formula (a1-1), R and Va ¹ are the same as R and Va ¹ in the aforementioned formula (a0-1-1).

In the aforementioned formula (a1-1), Ra ¹ is an acid dissociative group represented by the aforementioned formula (a1-r-1) or (a1-r-2).

In the aforementioned formula (a1-2), the n _a2 + 1-valent hydrocarbon group in Wa ¹ may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group not having aromaticity, and may be saturated or unsaturated, but saturation is generally preferred. The aforementioned aliphatic hydrocarbon group includes, for example: a straight-chain or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in its structure, or a straight-chain or branched aliphatic hydrocarbon group and an aliphatic hydrocarbon group containing a ring in its structure. The base obtained by combining hydrocarbon groups, etc. The aforementioned n _a2 +1 valence is preferably 2 to 4 valences, more preferably 2 or 3 valences.

The following are specific examples of the structural unit represented by the aforementioned formula (a1-1). In the following formulae, R ^α represents a hydrogen atom, a methyl group or a trifluoromethyl group.

The following are specific examples of the structural unit represented by the aforementioned formula (a1-2).

(A1) The structural unit (a1) which a component has may be 1 type, or 2 or more types may be sufficient. Structural unit (a1) is preferably a structural unit represented by the aforementioned formula (a1-1) from the viewpoint of easier improvement of characteristics (sensitivity, shape, etc.) during lithography using electron beams or EUV. Also, from the viewpoint of reducing the roughness, the acid dissociative group of Ra ¹ in the aforementioned formula (a1-1) is dissociated with the acid represented by the following general formula (a1-r2-11) or (a1-r2-21) Good sex.

[式(a1-r2-11)中，Ra’¹⁰ 為碳數1～10之烷基，Ra’¹¹¹ 表示與Ra’¹⁰ 鍵結的碳原子共同形成單環之脂肪族環式基之基。式(a1-r2-2)中，Ya為碳原子；Xb為與Ya共同形成單環之脂肪族烴基之基。該單環之脂肪族烴基所具有的氫原子之一部份或全部可被取代。Ra⁰¹ ～Ra⁰³ 各別獨立為氫原子、碳數1～10的1價之鏈狀飽和烴基或碳數3～20的1價之脂肪族環狀飽和烴基。該鏈狀飽和烴基及脂肪族環狀飽和烴基所具有的氫原子之一部份或全部可被取代。Ra⁰¹ ～Ra⁰³ 之2個以上可相互鍵結而形成環狀結構。＊表示鍵結鍵]。

[In the formula (a1-r2-11), Ra' ¹⁰ is an alkyl group with 1 to 10 carbon atoms, and Ra' ¹¹¹ represents an aliphatic cyclic group that forms a monocyclic ring together with the carbon atoms bonded to Ra' ¹⁰ . In the formula (a1-r2-2), Ya is a carbon atom; Xb is a group of an aliphatic hydrocarbon group forming a monocyclic ring together with Ya. Part or all of the hydrogen atoms of the monocyclic aliphatic hydrocarbon group may be substituted. Ra ⁰¹ to Ra ⁰³ are each independently a hydrogen atom, a monovalent chain saturated hydrocarbon group having 1 to 10 carbons, or a monovalent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbons. Part or all of the hydrogen atoms of the chain saturated hydrocarbon group and the aliphatic cyclic saturated hydrocarbon group may be substituted. Two or more of Ra ⁰¹ to Ra ⁰³ may be bonded to each other to form a ring structure. ＊ means a bonding key].

In the formula (a1-r2-11), Ra' ¹⁰ is the same as Ra' ¹⁰ in the aforementioned formula (a1-r2-1). In the formula (a1-r2-11), the monocyclic aliphatic hydrocarbon group formed by Ra' ¹¹¹ and the carbon atom bonded by Ra' ¹⁰ , and the monocyclic aliphatic hydrocarbon group of Ra' ³ in the formula (a1-r-1) The aliphatic hydrocarbon group in the formula group is preferably those listed above.

In the formula (a1-r2-21), the monocyclic aliphatic hydrocarbon group formed jointly by Xb and Ya can be enumerated such as: the cyclic monovalent hydrocarbon group in ^Ra'3 in the aforementioned formula (a1-r-1) A monocyclic aliphatic hydrocarbon group of a hydrocarbon group obtained by removing one or more hydrogen atoms, etc. The monocyclic aliphatic hydrocarbon group formed jointly by Xb and Ya may have a substituent. The substituent includes, for example, the same content as the substituent that the cyclic hydrocarbon group in ^Ra'3 above may have. Among them, the monocyclic aliphatic hydrocarbon group formed by Xb and Ya is preferably a group obtained by removing one hydrogen atom from monocyclic alkane, and a group obtained by removing one hydrogen atom from cyclopentane or cyclohexane The base is better. In formula (a1-r2-21), Ra ⁰¹ to Ra ⁰³ are the same as Ra ⁰¹ to Ra ⁰³ in formula (a1-r2-2).

The proportion of the structural unit (a1) in the component (A1) is preferably 5-70 mol%, preferably 5-65 mol%, relative to the total (100 mol%) of all structural units constituting the component (A1) % is better, and 5-50 mol% is more preferable. When the ratio of the structural unit (a1) is above the lower limit, resist patterns can be easily produced, and lithographic etching characteristics such as sensitivity, resolution, and roughness can be improved. Also, when it is below the upper limit, a balance with other structural units can be achieved.

Structural unit (a2): In addition to the structural unit (a0), the component (A1) may have a structure containing a lactone-containing cyclic group, a -SO ₂ --containing cyclic group, or a carbonate-containing cyclic group unit (a2). The lactone-containing cyclic group, -SO ₂ --containing cyclic group or carbonate-containing cyclic group of the structural unit (a2) has a structural unit (a2) that allows the component (A1) to form a suitable structure, For example, it can properly adjust the diffusion length of the acid, improve the adhesion between the resist film and the substrate, or moderately adjust the solubility during development, so that the lithographic etching characteristics can be improved.

The "lactone-containing cyclic group" means a cyclic group containing a -O-C(=O)--containing ring (lactone ring) in its ring skeleton. The lactone ring is counted as one ring, and when there are only lactone rings, it is called a monocyclic group, and when it has other ring structures, it is called a polycyclic group regardless of its structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group. The lactone-containing cyclic group in the structural unit (a2) is not particularly limited, and any component can be used. Specifically, for example, groups represented by the following general formulas (a2-r-1) to (a2-r-7), etc. respectively.

[式中，Ra’²¹ 各別獨立為氫原子、烷基、烷氧基、鹵素原子、鹵化烷基、羥基、-COOR”、-OC(=O)R”、羥烷基或氰基；R”為氫原子、烷基、含內酯之環式基、含碳酸酯之環式基，或含-SO₂ -之環式基。A”為可含有氧原子(-O-)或硫原子(-S-)的碳數1～5之伸烷基、氧原子或硫原子。n’為0～2之整數，m’為0或1]。

[wherein, ^Ra'21 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, an alkyl halide, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group or a cyano group; R" is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a -SO ₂ --containing cyclic group. A" may contain an oxygen atom (-O-) or sulfur Atom (-S-) is an alkylene group having 1 to 5 carbon atoms, an oxygen atom or a sulfur atom. n' is an integer of 0 to 2, m' is 0 or 1].

In the aforementioned formulas (a2-r-1) to (a2-r-7), the alkyl group in ^Ra'21 is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group etc. are mentioned. Among these, methyl or ethyl is preferable, and methyl is particularly preferable. The alkoxy group in ^Ra'21 is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably linear or branched. Specifically, for example, in the aforementioned ^Ra'21 , an alkyl group as an alkyl group, a group obtained by bonding to an oxygen atom (-O-), and the like are listed. The halogen atoms in Ra' ²¹ include, for example, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., and fluorine atoms are preferred. The halogenated alkyl group in ^Ra'21 includes, for example, a group obtained by substituting a part or all of the hydrogen atoms of the alkyl group in the aforementioned ^Ra'21 with the aforementioned halogen atoms. The halogenated alkyl group is preferably a fluorinated alkyl group, particularly preferably a perfluoroalkyl group.

In -COOR" and -OC(=O)R" in Ra' ²¹ , any R" is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a - Cyclic group of SO ₂ -. The alkyl group in R" can be linear, branched or cyclic, and the number of carbon atoms is preferably 1-15. When R" is a linear or branched alkyl group, it preferably has 1 to 10 carbons, more preferably 1 to 5 carbons, especially methyl or ethyl. R" is cyclic In the case of an alkyl group, the number of carbons is preferably 3-15, more preferably 4-12, and more preferably 5-10. Specifically, examples include: groups obtained by removing one or more hydrogen atoms from unsubstituted monocyclic alkanes that may be substituted by fluorine atoms or fluorinated alkyl groups; A group obtained by removing one or more hydrogen atoms from polycyclic alkanes such as alkanes and tetracyclic alkanes. More specifically, examples include: groups obtained by removing one or more hydrogen atoms from monocyclic alkanes such as cyclopentane and cyclohexane; A group obtained by removing one or more hydrogen atoms from polycyclic alkanes such as alkanes and tetracyclododecanes, etc. The lactone-containing cyclic group in R" and the respective groups represented by the aforementioned general formulas (a2-r-1) to (a2-r-7) have the same content, etc. The carbonate-containing group in R" The cyclic group is the same as the carbonate-containing cyclic group described later, and specific examples thereof include groups represented by the general formulas (ax3-r-1) to (ax3-r-3). The cyclic group containing -SO ₂ - in R" has the same content as the cyclic group containing -SO ₂ - described later. Specifically, it can be listed as: general formula (a5-r-1)～(a5 -r-4) the groups represented separately, etc. The hydroxyalkyl group in ^Ra'21 is preferably one with 1 to 6 carbon atoms, specifically, for example: at least one hydrogen of the alkyl group in the above-mentioned ^Ra'21 A group in which an atom is substituted by a hydroxyl group, etc.

In the aforementioned general formulas (a2-r-2), (a2-r-3), and (a2-r-5), the alkylene group with 1 to 5 carbons in A" can be linear or branched The alkylene group is preferred, such as: methylene group, ethylidene group, n-propylidene group, isopropylidene group, etc. When the alkylene group contains an oxygen atom or a sulfur atom, its specific example is as follows: The group obtained by interposing -O- or -S- at the end of the alkyl group or between carbon atoms, such as: -O-CH ₂ -, -CH ₂ -O-CH ₂ -, -S-CH ₂ -, -CH ₂ -S-CH ₂ - etc. A" is preferably an alkylene group with 1 to 5 carbons or -O-, preferably an alkylene group with 1 to 5 carbons, and a methylene group is the most good.

Specific examples of groups represented by the general formulas (a2-r-1) to (a2-r-7) are listed below.

"Cyclic group containing -SO ₂ -" means a cyclic group containing a ring containing -SO ₂ - in its ring skeleton, specifically, it is formed by the sulfur atom (S) in -SO ₂ - A cyclic group that is part of the ring skeleton of the cyclic group. It is counted by counting a ring containing -SO ₂ - in its ring skeleton as one ring. When it is only this ring, it is called a monocyclic group. When it has other ring structures, it is called a polycyclic group regardless of its structure. Formula base. The cyclic group containing -SO ₂ - may be a monocyclic group or a polycyclic group. A cyclic group containing -SO ₂ -, especially a cyclic group containing -O-SO ₂ - in its ring skeleton, that is, the -OS- containing -O-SO ₂ - is formed as a part of the ring skeleton A cyclic group with a part of sultone ring is preferred. The cyclic group containing -SO ₂ - includes, for example, groups respectively represented by the following general formulas (a5-r-1) to (a5-r-4), etc. more specifically.

[式中，Ra’⁵¹ 各別獨立為氫原子、烷基、烷氧基、鹵素原子、鹵化烷基、羥基、-COOR”、-OC(=O)R”、羥烷基或氰基。R”為氫原子、烷基、含內酯之環式基、含碳酸酯之環式基，或含-SO₂ -之環式基。A”為可含有氧原子或硫原子的碳數1～5之伸烷基、氧原子或硫原子。 n’為0～2之整數]。

[wherein, ^Ra'51 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, an alkyl halide, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group or a cyano group. R" is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a -SO ₂ --containing cyclic group. A" is a carbon number 1 that may contain an oxygen atom or a sulfur atom ~5 alkylene groups, oxygen atoms or sulfur atoms. n' is an integer from 0 to 2].

In the aforementioned general formulas (a5-r-1) to (a5-r-2), A" is the same as in the aforementioned general formulas (a2-r-2), (a2-r-3), and (a2-r-5) "A" has the same content. The alkyl group, alkoxyl group, halogen atom, halogenated alkyl group, -COOR", -OC(=O)R", and hydroxyalkyl group in Ra' ⁵¹ are respectively related to the aforementioned general formula (a2-r-1)～( The ones listed in the description of ^Ra'21 in a2-r-7) are the same contents and the like. Specific examples of groups represented by the general formulas (a5-r-1) to (a5-r-4) are listed below. "Ac" in the formula means an acetyl group.

The "carbonate-containing cyclic group" means a cyclic group containing a ring (carbonate ring) containing -O-C(=O)-O- in its ring skeleton. The carbonate ring is counted as one ring, and when there is only a carbonate ring, it is called a monocyclic group, and when it has other ring structures, it is called a polycyclic group regardless of the structure. The carbonate-containing cyclic group may be a monocyclic group or a polycyclic group. The cyclic group containing a carbonate ring is not particularly limited, and arbitrary components can be used. Specifically, groups represented by the following general formulas (ax3-r-1) to (ax3-r-3), etc. are mentioned, respectively.

[式中，Ra’^x31 各別獨立為氫原子、烷基、烷氧基、鹵素原子、鹵化烷基、羥基、-COOR”、-OC(=O)R”、羥烷基或氰基。R”為氫原子、烷基、含內酯之環式基、含碳酸酯之環式基，或含-SO₂ -之環式基。A”為可含有氧原子或硫原子的碳數1～5之伸烷基、氧原子或硫原子。p’為0～3之整數，q’為0或1]。

[In the formula, ^Ra'x31 are each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group or a cyano group. R" is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a -SO ₂ --containing cyclic group. A" is a carbon number 1 that may contain an oxygen atom or a sulfur atom ~5 alkylene groups, oxygen atoms or sulfur atoms. p' is an integer of 0 to 3, and q' is 0 or 1].

In the aforementioned general formula (ax3-r-2) ~ (ax3-r-3), A" is the same as in the aforementioned general formula (a2-r-2), (a2-r-3), (a2-r-5) "A" has the same content. The alkyl group, alkoxyl group, halogen atom, halogenated alkyl group, -COOR ", -OC(=O)R ", hydroxyalkyl group in Ra' ³¹ are respectively the same as the aforementioned general formula (a2-r-1)～( The ones listed in the description of ^Ra'21 in a2-r-7) are the same contents and the like. Specific examples of groups represented by the general formulas (ax3-r-1) to (ax3-r-3) are listed below.

Among the structural units (a2), structural units derived from acrylates in which hydrogen atoms bonded to carbon atoms at the α-position can be replaced by substituents are preferred. Preferable specific examples of the structural unit (a2) include, for example, structural units represented by the following general formula (a2-1).

[式中，R為氫原子、碳數1～5之烷基或碳數1～5之鹵化烷基；Ya²¹ 為單鍵或2價之連結基。La²¹ 為-O-、-COO-、 -CON(R’)-、-OCO-、-CONHCO-或-CONHCS-，R’表示氫原子或甲基。其中，La²¹ 為-O-時，Ya²¹ 不為-CO-。Ra²¹ 為含內酯之環式基、含-SO₂ -之環式基或含碳酸酯之環式基]。

[In the formula, R is a hydrogen atom, an alkyl group with 1 to 5 carbons, or a halogenated alkyl group with 1 to 5 carbons; Ya ²¹ is a single bond or a divalent linking group. La ²¹ is -O-, -COO-, -CON(R')-, -OCO-, -CONHCO- or -CONHCS-, and R' represents a hydrogen atom or a methyl group. Wherein, when La ²¹ is -O-, Ya ²¹ is not -CO-. Ra ²¹ is a lactone-containing cyclic group, a -SO ₂ --containing cyclic group, or a carbonate-containing cyclic group].

In the above-mentioned formula (a2-1), R is the same as above. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbons, or a fluorinated alkyl group having 1 to 5 carbons, and particularly preferably a hydrogen atom or a methyl group in terms of industrial availability.

In the aforementioned formula (a2-1), the divalent linking group of Ya ²¹ is not particularly limited, and a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a heteroatom, etc. are preferred. instantiate.

Examples of the divalent hydrocarbon group in Ya ²¹ include the same groups as those listed in the description of the divalent hydrocarbon group in Va ¹ in the above formula (a1-1). The substituent that the divalent hydrocarbon group in Ya ²¹ may have includes, for example, an alkyl group having 1 to 5 carbons, an alkoxy group, a halogen atom, a halogenated alkyl group having 1 to 5 carbons, a hydroxyl group, and a carbonyl group.

In Ya ²¹ , preferred groups of divalent linking groups containing heteroatoms include: -O-, -C(=O)-O-, -C(=O)-, -OC(=O )-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)-(H can be replaced by substituents such as alkyl, acyl, etc.), -S-, - S(=O) ₂ -, -S(=O) ₂ -O-, general formula -Y ²¹ -OY ²² -, -Y ²¹ -O-, -Y ²¹ -C(=O)-O-, - C(=O)-OY ²¹ -, -[Y ²¹ -C(=O)-O] _m” -Y ²² -, -Y ²¹ -OC(=O)-Y ²² - or -Y ²¹ -S( A group represented by =O) ₂ -OY ²² - [wherein, Y ²¹ and Y ²² are each independently a divalent hydrocarbon group that may have a substituent, O is an oxygen atom, m" is an integer of 0 to 3], etc. . The aforementioned divalent linking groups containing heteroatoms are -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, -NH-C(=NH)- When , this H may be substituted by a substituent such as an alkyl group or an acyl group. The substituent (alkyl group, acyl group, etc.) preferably has 1-10 carbon atoms, more preferably 1-8 carbon atoms, and particularly preferably 1-5 carbon atoms. General formula -Y ²¹ -OY ²² -, -Y ²¹ -O-, -Y ²¹ -C(=O)-O-, -C(=O)-OY ²¹ -, -[Y ²¹ -C(=O )-O] _m” -Y ²² -, -Y ²¹ -OC(=O)-Y ²² - or -Y ²¹ -S(=O) ₂ -OY ²² -, Y ²¹ and Y ²² are independently A divalent hydrocarbon group that may have a substituent. The divalent hydrocarbon group is, for example, the same as that listed above in the description of the divalent linking group (divalent hydrocarbon group that may have a substituent). Y ²¹ The linear aliphatic hydrocarbon group is preferred, the linear alkylene group is preferred, the linear alkylene group with 1 to 5 carbons is more preferred, and the methylene or ethylene group is preferred. Especially preferred. Y ²² is preferably a straight-chain or branched aliphatic hydrocarbon group, preferably a methyl group, an ethyl group or an alkyl group. The alkyl group in the alkyl group is represented by the number of carbons A linear alkyl group with 1 to 5 carbon atoms is preferred, a linear alkyl group with 1 to 3 carbon atoms is preferred, and methyl is the most preferred. Formula -[Y ²¹ -C(=O)-O ] _m" -Y ²² - In the base represented, m" is an integer of 0 to 3, preferably an integer of 0 to 2, preferably 0 or 1, and particularly preferably 1. That is, the formula- The group represented by [Y ²¹ -C(=O)-O] _m” -Y ²² - is particularly preferably represented by the formula -Y ²¹ -C(=O)-OY ²² -. Among them, the group represented by the formula -(CH ₂ ) _a' -C(=O)-O-(CH ₂ ) _b' - is preferable. In the formula, a' is an integer of 1-10, preferably an integer of 1-8, more preferably an integer of 1-5, more preferably 1 or 2, and most preferably 1. b' is an integer of 1-10, preferably an integer of 1-8, more preferably an integer of 1-5, more preferably 1 or 2, and most preferably 1.

Ya ²¹ is preferably a single bond, an ester bond [-C(=O)-O-], an ether bond (-O-), a linear or branched alkylene group, or a combination thereof.

In the aforementioned formula (a2-1), La ²¹ is -O-, -COO-, -CON(R')-, -OCO-, -CONHCO- or -CONHCS-. R' represents a hydrogen atom or a methyl group. Wherein, when La ²¹ is -O-, Ya ²¹ is not -CO-.

In the aforementioned formula (a2-1), Ra ²¹ is a lactone-containing cyclic group, a -SO ₂ --containing cyclic group, or a carbonate-containing cyclic group. The lactone-containing cyclic group, -SO ₂ -containing cyclic group, and carbonate-containing cyclic group in Ra ²¹ are represented by the above general formulas (a2-r-1)~(a2-r-7) The groups represented separately, the groups represented by the general formulas (a5-r-1) to (a5-r-4), the groups represented by the general formulas (ax3-r-1) to (ax3-r-3) The basis of different representation is a better example. Among them, Ra ²¹ is preferably a cyclic group containing lactone or a cyclic group containing -SO ₂ -, and the aforementioned general formula (a2-r-1), (a2-r-2), (a2-r The groups represented by -6) or (a5-r-1) are preferable. Specifically, with the aforementioned chemical formulas (r-lc-1-1) ~ (r-lc-1-7), (r-lc-2-1) ~ (r-lc-2-18), (r- Any one of the groups represented by lc-6-1), (r-sl-1-1), and (r-sl-1-18) respectively is preferable.

(A1) The structural unit (a2) which a component has may be 1 type, or 2 or more types may be sufficient. When the component (A1) has a structural unit (a2), the ratio of the structural unit (a2) to the total (100 mol%) of all structural units constituting the component (A1) is preferably 1 to 80 mol%. , preferably 3-70 mol%, more preferably 5-60 mol%, more preferably 5-50 mol%. When the ratio of the structural unit (a2) is more than the lower limit value of the above-mentioned preferred range, based on the above-mentioned effect, when the structural unit (a2) is contained, a sufficient effect can be obtained. On the other hand, when the proportion of the structural unit (a2) is below the upper limit of the above-mentioned preferred range, it is easy to achieve a balance with other structural units, so that various lithographic etching properties can be improved.

Structural unit (a3): The component (A1) may have, in addition to the structural unit (a0), a structural unit (a3) containing an aliphatic hydrocarbon group containing a polar group (wherein, it corresponds to any of the above-mentioned structural unit (a1) and structural unit (a2) except for a structural unit). When the component (A1) has a structural unit (a3) with an appropriate structure, for example, it can properly adjust the diffusion length of the acid, improve the adhesion of the resist film to the substrate, moderately adjust the solubility during development, and improve the etching resistance. The effects of properties, etc., can make the lithographic etching properties more favorable.

Polar groups include, for example, hydroxyl groups, cyano groups, carboxyl groups, and hydroxyalkyl groups in which some of the hydrogen atoms of alkyl groups are replaced by fluorine atoms. Hydroxyl groups are particularly preferred. The aliphatic hydrocarbon group includes, for example, a straight-chain or branched-chain hydrocarbon group (preferably an alkylene group) having 1 to 10 carbon atoms, or a cyclic aliphatic hydrocarbon group (cyclic group). The cyclic group may be a monocyclic group or a polycyclic group, and may be appropriately selected and used among many proposed components in the resin for the resist composition for ArF excimer laser, for example. The cyclic group is preferably a polycyclic group, preferably having 7 to 30 carbon atoms. Among them, the structural unit derived from aliphatic polycyclic acrylate containing hydroxyl, cyano, carboxyl, or hydroxyalkyl containing a part of hydrogen atoms replaced by fluorine atoms is better. Examples of the polycyclic group include groups obtained by removing two or more hydrogen atoms from bicyclic alkanes, tricyclic alkanes, tetracyclic alkanes, and the like. Specific examples thereof include groups obtained by removing two or more hydrogen atoms from polycyclic alkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Among these polycyclic groups, the group obtained by removing two or more hydrogen atoms from adamantane, the group obtained by removing two or more hydrogen atoms from norbornane, and the group obtained by removing two or more hydrogen atoms from tetracyclododecane The base derived from more than one hydrogen atom is industrially preferred.

The structural unit (a3) is not particularly limited as long as it contains a polar group-containing aliphatic hydrocarbon group, and any component can be used. The structural unit (a3) is preferably a structural unit derived from an acrylic ester in which a hydrogen atom bonded to a carbon atom at the α position can be replaced by a substituent, and a structural unit containing an aliphatic hydrocarbon group containing a polar group. Structural unit (a3), when the hydrocarbon group in the aliphatic hydrocarbon group containing a polar group is a linear or branched hydrocarbon group with 1 to 10 carbons, the structural unit derived from hydroxyethyl acrylate is preferred, When the hydrocarbon group is a polycyclic group, the structural unit represented by the following formula (a3-1), the structural unit represented by the formula (a3-2), and the structural unit represented by the formula (a3-3) are preferably exemplified .

[式中，R與前述為相同內容，j為1～3之整數，k為1～3之整數，t’為1～3之整數，l為1～5之整數，s為1～3之整數]。

[In the formula, R is the same as above, j is an integer of 1 to 3, k is an integer of 1 to 3, t' is an integer of 1 to 3, l is an integer of 1 to 5, s is an integer of 1 to 3 integer].

In formula (a3-1), j is preferably 1 or 2, more preferably 1. When j is 2, the hydroxyl group is preferably bonded to the 3-position and 5-position of the adamantyl group. When j is 1, the hydroxyl group is preferably bonded to the third position of the adamantyl group. Preferably j is 1, and the hydroxyl group is particularly preferably bonded to the 3rd position of the adamantyl group.

In formula (a3-2), k is preferably 1. The cyano group is preferably bonded to the 5- or 6-position of the norbornyl group.

In formula (a3-3), t' is preferably 1. l is preferably 1. s is preferably 1. These are preferably those in which a 2-norbornyl group or a 3-norbornyl group is bonded to the carboxyl terminal of acrylic acid. The fluorinated alkanol is preferably bonded to the 5 or 6 position of the norbornyl group.

(A1) The structural unit (a3) which a component has may be 1 type or 2 or more types. When the component (A1) has a structural unit (a3), the ratio of the structural unit (a3) to the total (100 mol%) of all structural units constituting the component (A1) is preferably 1 to 50 mol%. , preferably 3-40 mol%, more preferably 5-30 mol%, and particularly preferably 10-30 mol%. When the proportion of the structural unit (a3) is more than the preferable lower limit, based on the above-mentioned effects, sufficient effects can be obtained when the structural unit (a3) is contained. On the other hand, when the proportion of the structural unit (a3) is below the preferred upper limit, it is easy to achieve a balance with other structural units, and various lithographic etching properties can be improved.

Structural unit (a4): The component (A1) may further have a structural unit (a4) containing a non-acid dissociative aliphatic cyclic group in addition to the structural unit (a0). When the component (A1) has the structural unit (a4), the dry etching resistance of the formed resist pattern can be improved. Moreover, the hydrophobicity of (A) component can also be raised. The improvement of hydrophobicity, especially in the case of solvent development process, can be expected to improve resolution, resist pattern shape, etc. The "non-acid dissociative cyclic group" in the structural unit (a4) refers to when an acid is generated in the resist composition by exposure (for example: generated by the structural unit or (B) component that generates an acid by exposure acid), a cyclic group that remains in the structural unit without dissociation even when subjected to the action of the acid.

The structural unit (a4) is preferably, for example, a structural unit derived from an acrylate containing a non-acid-dissociable aliphatic cyclic group. As the cyclic group, many conventionally known groups used in resin components of resist compositions such as those for ArF excimer lasers and KrF excimer lasers (preferably for ArF excimer lasers) can be used. The cyclic group is particularly preferably at least one selected from the group consisting of tricyclodecanyl, adamantyl, tetracyclododecyl, isobornyl and norbornyl from the standpoint of industrial availability. These polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent. As for the structural unit (a4), specifically, structural units represented by the following general formulas (a4-1) to (a4-7), etc. are exemplified, for example.

[式中，R^α 與前述為相同內容]。

[In the formula, R ^α is the same as the above].

(A1) The structural unit (a4) which a component has may be 1 type or 2 or more types. When the component (A1) has a structural unit (a4), the ratio of the structural unit (a4) to the total (100 mol%) of all structural units constituting the component (A1) is preferably 1 to 40 mol%. , preferably 5-20 mol%. When the proportion of the structural unit (a4) is more than the preferable lower limit value, based on the above-mentioned effects, when the structural unit (a4) is contained, sufficient effects can be obtained. On the other hand, when the proportion of the unit (a4) is below the preferred upper limit, it is easy to achieve a balance with other structural units, and to make various lithographic etching properties better.

Structural units derived from styrene or its derivatives (structural unit (st)): "Styrene" is a concept including styrene and a hydrogen atom at the alpha position of styrene is substituted with a substituent such as an alkyl group or a halogenated alkyl group. Here, the alkyl group as the substituent includes, for example, an alkyl group having 1 to 5 carbon atoms, and the halogenated alkyl group as the substituent includes, for example, a halogenated alkyl group having 1 to 5 carbon atoms. "Styrene derivative" means a substituent bonded to the benzene ring of styrene in which the hydrogen atom at the α position may be substituted by a substituent. Also, the α-position (carbon atom at the α-position) means the carbon atom bonded to the benzene ring unless otherwise specified. "Structural unit derived from styrene" and "structural unit derived from styrene derivative" mean a structural unit formed by cleavage of the ethylenic double bond of styrene or a styrene derivative. (A1) The structural unit (st) which a component has may be 1 type or 2 or more types. When the component (A1) has a structural unit (st), the proportion of the structural unit (st) is preferably 1 to 30 mol% relative to the total of all structural units constituting the component (A1) (100 mol%), 3-20 mol% is preferred.

In the resist composition of this embodiment, the component (A1) preferably contains a copolymer (component (A1-1)) having the structural unit (a0) and other structural units if necessary. The (A1-1) component, specifically, can include, for example: a polymer compound composed of a repeating structure of a structural unit (a0) and a structural unit (a10), a structural unit (a0) and a structural unit (a10) and a structural A polymer compound composed of a repeating structure of the unit (a2), a polymer compound composed of a repeating structure of the structural unit (a0) and the structural unit (a10) and the structural unit (a3), etc. are exemplified.

≪(A2) Ingredients≫ In the resist composition of the present embodiment, component (A) may be used in combination with a substrate component (hereinafter, also referred to as "substrate component") that does not correspond to the aforementioned component (A1) and whose solubility in a developer solution changes through the action of an acid. (A2) Ingredients"). The component (A2) is not particularly limited, and it can be arbitrarily selected from many components conventionally known as substrate components for chemically amplified resist compositions. (A2) As a component, one kind of high molecular weight compound or low molecular weight compound may be used alone, or two or more kinds may be used in combination.

(A1) The mass average molecular weight (Mw) of the component (polystyrene conversion basis of gel permeation chromatography (GPC)) is not particularly limited, and is preferably 1,000-50,000, more preferably 2,000-30,000 , preferably 3000-20000. When the Mw of the component (A1) is below the preferred upper limit of the range, it has sufficient solubility to the resist solvent when used as a resist, and when it is above the preferred lower limit of the range, it can have good The dry etching resistance or the cross-sectional shape of the resist pattern. (A1) The degree of dispersion (Mw/Mn) of the components is not particularly limited, but generally it is preferably about 1.0-4.0, more preferably about 1.0-3.0, and most preferably about 1.0-2.5. Also, Mn represents a number average molecular weight.

(A1) The component may be used individually by 1 type, and may use it in combination of 2 or more types. Among components (A), the ratio of component (A1) to the total mass of component (A) is preferably at least 25% by mass, more preferably at least 50% by mass, more preferably at least 75% by mass, and It may be 100% by mass. When the ratio is 25% by mass or more, it is possible to easily form a resist pattern having various lithographic etching properties such as high sensitivity or improved roughness.

In the resist composition of this embodiment, the content of component (A) can be appropriately adjusted according to the thickness of the resist film to be formed.

＜Component (B)＞ ・(B1) Ingredients (B) The component is an acid generator component which generates acid by exposure. In the resist composition of the present embodiment, component (B) contains a compound (b-1) represented by the following general formula (b-1) (hereinafter also referred to as "component (b-1)") ), the compound (b-2) represented by the following general formula (b-2) (hereinafter also referred to as "(b-2) component") and the compound represented by the following general formula (b-3) ( At least one selected from the group consisting of b-3) (hereinafter, also referred to as "(b-3) component") (hereinafter, also collectively referred to as "(B1) component").

[式中，R¹⁰¹ 、R¹⁰⁴ 及R¹⁰⁶ ，各別獨立為含有可具有取代基的芳香環之烴基；R¹⁰⁵ 、R¹⁰⁷ 及R¹⁰⁸ ，各別獨立為可具有取代基之環式基、可具有取代基之鏈狀烷基，或可具有取代基之鏈狀烯基；R¹⁰² 為氟原子或碳數1～5之氟化烷基。Y¹⁰¹ 為單鍵或含有氧原子的2價之連結基。 V¹⁰¹ ～V¹⁰³ 各別獨立為單鍵、伸烷基或氟化伸烷基。L¹⁰¹ ～L¹⁰² 各別獨立為單鍵或氧原子。L¹⁰³ ～L¹⁰⁵ 各別獨立為單鍵、-CO-或-SO₂ -。m為1以上之整數，且M’^m+ 為m價之鎓陽離子]。

[wherein, R ¹⁰¹ , R ¹⁰⁴ and R ¹⁰⁶ are each independently a hydrocarbon group containing an aromatic ring that may have a substituent; R ¹⁰⁵ , R ¹⁰⁷ and R ¹⁰⁸ are each independently a cyclic group that may have a substituent, A chained alkyl group that may have a substituent, or a chained alkenyl group that may have a substituent; R ¹⁰² is a fluorine atom or a fluorinated alkyl group with 1 to 5 carbon atoms. ^Y101 is a single bond or a divalent linking group containing an oxygen atom. V ¹⁰¹ to V ¹⁰³ are each independently a single bond, an alkylene group or a fluorinated alkylene group. L ¹⁰¹ to L ¹⁰² are each independently a single bond or an oxygen atom. L ¹⁰³ to L ¹⁰⁵ are each independently a single bond, -CO- or -SO ₂ -. m is an integer of 1 or more, and M' ^m+ is an m-valent onium cation].

{Anionic part} ・In the anionic part of the component (b-1), in the formula (b-1), R ¹⁰¹ is a hydrocarbon group having an aromatic ring which may have a substituent. The aromatic ring-containing hydrocarbon group of R ¹⁰¹ preferably has 3-30 carbons, more preferably 5-30 carbons, more preferably 5-20 carbons, and particularly preferably 6-18 carbons. However, the carbon number does not include the carbon number in the substituent. The aromatic ring possessed by the aromatic hydrocarbon group in R ¹⁰¹ specifically includes: benzene, stilbene, naphthalene, anthracene, phenanthrene, biphenyl, or some of the carbon atoms constituting these aromatic rings are replaced by heteroatoms Aromatic heterocycles obtained by substitution, etc. The hetero atom in the aromatic heterocycle includes, for example, an oxygen atom, a sulfur atom, a nitrogen atom, and the like. The hydrocarbon group containing an aromatic ring of R ¹⁰¹ specifically includes, for example, a group obtained by removing one hydrogen atom from the aforementioned aromatic ring (aryl group: such as phenyl, naphthyl, etc.), among the hydrogen atoms of the aforementioned aromatic ring, One of them is substituted by an alkylene group (such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc. aralkyl, etc.), a group obtained by removing one hydrogen atom from a condensed ring obtained by condensing the aforementioned aromatic ring on a crosslinked aliphatic ring of bicycloheptane, bicyclooctane, etc. The carbon number of the aforementioned alkylene group (alkane chain in the aralkyl group) is preferably 1-4, more preferably 1-2, and particularly preferably 1.

In the aromatic ring-containing hydrocarbon group of R ¹⁰¹ , the substituent that the aromatic ring may have includes, for example, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, and a nitro group. The alkyl group as a substituent is preferably an alkyl group with 1 to 5 carbons or a cycloalkyl group with 3 to 6 carbons, methyl, ethyl, propyl, n-butyl, tert-butyl, cycloalkyl Pentyl and cyclohexyl are preferred. The alkoxy group as a substituent is preferably an alkoxy group with 1 to 5 carbon atoms, such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert -Butoxy is preferred, and methoxy and ethoxy are most preferred. The halogen atom as a substituent includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred. The halogenated alkyl group as a substituent is an alkyl group with 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, tert-butyl, etc., where part or all of the hydrogen atoms are replaced by the aforementioned A group obtained by substituting a halogen atom, etc. The carbonyl group as a substituent is a group substituting a methylene group (-CH ₂ -) constituting a cyclic hydrocarbon group. Among them, in the hydrocarbon group containing an aromatic ring in ^R101 , the substituent that the aromatic ring may have is preferably tert-butyl, hydroxyl or cyclohexyl.

In formula (b-1), Y ¹⁰¹ is a single bond or a divalent linking group containing an oxygen atom. When Y ¹⁰¹ is a divalent linking group containing an oxygen atom, this Y ¹⁰¹ may contain atoms other than an oxygen atom. Atoms other than oxygen atoms, such as carbon atoms, hydrogen atoms, sulfur atoms, nitrogen atoms, etc. Divalent linking groups containing oxygen atoms, such as: oxygen atom (ether bond: -O-), ester bond (-C(=O)-O-), oxycarbonyl (-OC(=O) -), amide bond (-C(=O)-NH-), carbonyl (-C(=O)-), carbonate bond (-OC(=O)-O-) and other non-hydrocarbon systems A linking group containing an oxygen atom; a combination of the non-hydrocarbon-based linking group containing an oxygen atom and an alkylene group, etc. In this combination, a sulfonyl group (-SO ₂ -) may be further bonded. The divalent linking group containing an oxygen atom is, for example, linking groups represented by the following general formulas (y-al-1) to (y-al-9), respectively.

[式中，V’¹⁰¹ 為單鍵或碳數1～5之伸烷基，V’¹⁰² 為碳數1～30的2價之飽和烴基]。

[wherein, ^V'101 is a single bond or an alkylene group with 1 to 5 carbons, and ^V'102 is a divalent saturated hydrocarbon group with 1 to 30 carbons].

The divalent saturated hydrocarbon group in ^V'102 is preferably an alkylene group with 1 to 30 carbons, more preferably an alkylene group with 1 to 10 carbons, and more preferably an alkylene group with 1 to 5 carbons. good.

The alkylene groups in ^V'101 and ^V'102 may be linear or branched, and preferably linear. The alkylene groups in V' ¹⁰¹ and V' ¹⁰² specifically include: methylene [-CH ₂ -]; -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, - C(CH ₃ ) ₂ -, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ - etc. Alkylmethylene; Ethyl[-CH ₂ CH ₂ -]; -CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ - , -CH(CH ₂ CH ₃ )CH ₂ - and other alkyl ethylidene groups; trimethyl(n-propylidene)[-CH ₂ CH ₂ CH ₂ -]; -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ - and other alkyltrimethylene; Tetramethyl[-CH ₂ CH ₂ CH ₂ CH ₂ -]; -CH(CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ -, etc., alkyl tetramethylene; pentamethyl[-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -], etc. Also, in ^V'101 or ^V'102 , some of the methylene groups in the aforementioned alkylene group may be substituted by a divalent aliphatic ring group having 5 to 10 carbon atoms. The aliphatic cyclic group is obtained by removing 1 from the cyclic aliphatic hydrocarbon group (monocyclic alicyclic hydrocarbon group, polycyclic alicyclic hydrocarbon group) in R ¹⁰¹ in the aforementioned formula (b-1). A divalent group derived from one hydrogen atom is preferred, and cyclohexylene, 1,5-adamantyl or 2,6-adamantyl is more preferred.

Y ¹⁰¹ is preferably a divalent linking group containing an ester bond, or a divalent linking group containing an ether bond, represented by the above formulas (y-al-1) to (y-al-5) respectively A linker is preferred.

In the formula (b-1), V ¹⁰¹ is a single bond, an alkylene group or a fluorinated alkylene group. The alkylene group and fluorinated alkylene group in V ¹⁰¹ preferably have 1-4 carbon atoms. The fluorinated alkylene group in ^V101 is a group obtained by substituting part or all of the hydrogen atoms of the alkylene group in ^V101 with fluorine atoms, etc. Among them, V ¹⁰¹ is preferably a single bond, or a fluorinated alkylene group having 1 to 4 carbon atoms.

In formula (b-1), R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbons. R ¹⁰² is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbons, more preferably a fluorine atom.

・In the anion moiety formula (b-2) of the component (b-2), R ¹⁰⁴ to R ¹⁰⁵ are independently cyclic groups that may have substituents, chain alkyl groups that may have substituents, or may have Chain alkenyl substituent. However, R ¹⁰⁴ and R ¹⁰⁵ may be bonded to each other to form a ring.

Cyclic groups that may have substituents: The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group not having aromaticity. In addition, the aliphatic hydrocarbon group may be saturated or unsaturated, but usually saturated is preferred.

The aromatic hydrocarbon groups in R ¹⁰⁴ to R ¹⁰⁵ are hydrocarbon groups having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbons, more preferably 5 to 30 carbons, more preferably 5 to 20 carbons, particularly preferably 6 to 15 carbons, and 6 to 10 carbons. for the best. However, the carbon number does not include the carbon number in the substituent. The aromatic rings possessed by the aromatic hydrocarbon groups in R ¹⁰⁴ to R ¹⁰⁵ specifically include: benzene, fennel, naphthalene, anthracene, phenanthrene, biphenyl, or some of the carbon atoms constituting these aromatic rings Aromatic heterocycles substituted by heteroatoms, etc. The hetero atom in the aromatic heterocycle includes, for example, an oxygen atom, a sulfur atom, a nitrogen atom, and the like. The aromatic hydrocarbon groups in R ¹⁰⁴ to R ¹⁰⁵ specifically include groups obtained by removing one hydrogen atom from the aforementioned aromatic rings (aryl groups: such as phenyl, naphthyl, etc.), hydrogen atoms of the aforementioned aromatic rings, A group in which one of the atoms is substituted by an alkylene group (such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl etc. aralkyl, etc.) etc. The carbon number of the aforementioned alkylene group (alkane chain in the aralkyl group) is preferably 1-4, more preferably 1-2, and particularly preferably 1.

The cyclic aliphatic hydrocarbon groups in R ¹⁰⁴ to R ¹⁰⁵ include, for example, aliphatic hydrocarbon groups containing rings in their structures. The aliphatic hydrocarbon group containing a ring in the structure includes, for example: an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), an alicyclic hydrocarbon group bonded to a straight chain or a branched chain A group obtained at the end of an aliphatic hydrocarbon group, a group obtained by interposing an alicyclic hydrocarbon group in the middle of a linear or branched aliphatic hydrocarbon group, etc. The aforementioned alicyclic hydrocarbon group preferably has 3-20 carbon atoms, more preferably 3-12 carbon atoms. The aforementioned alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocyclic alkane. The monocyclic alkanes preferably have 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycyclic alkane, and the polycyclic alkane preferably has 7 to 30 carbon atoms. Among them, the polycyclic alkanes are: adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc., which have polycyclic skeletons with cross-linked ring systems; A polycyclic alkane having a polycyclic skeleton of a condensed ring system such as a cyclic group of a cholesterol skeleton is preferable.

Among them, the cyclic aliphatic hydrocarbon group in R ¹⁰⁴ ~ R ¹⁰⁵ is preferably a group obtained by removing one or more hydrogen atoms from a monocyclic alkane or a polycyclic alkane, and a group obtained by removing 1 hydrogen atom from a polycyclic alkane A group derived from hydrogen atoms is preferred, adamantyl and norbornyl are particularly preferred, and adamantyl is most preferred.

A linear or branched aliphatic hydrocarbon group that can be bonded to an alicyclic hydrocarbon group, preferably with 1 to 10 carbons, more preferably 1 to 6 carbons, more preferably 1 to 4 carbons , with carbon numbers of 1 to 3 being particularly preferred. Straight-chain aliphatic hydrocarbon groups are preferably straight-chain alkylene groups. Specifically, examples include: methylene [-CH ₂ -], ethylene [-(CH ₂ ) ₂ -], Trimethyl[-(CH ₂ ) ₃ -], Tetramethyl[-(CH ₂ ) ₄ -], Pentamethyl[-(CH ₂ ) ₅ -], etc. Branched-chain aliphatic hydrocarbon groups are preferably branched-chain alkylene groups. Specifically, examples include: -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ -, etc. ; -CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C( CH ₂ CH ₃ ) ₂ -CH ₂ - and other alkyl ethylene groups; -CH(CH ₃ ) CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ ) CH ₂ - and other alkyl trimethyl groups; -CH (CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ -, alkylene such as tetramethyl, alkylene such as tetramethyl, etc. The alkyl group in the alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

Also, the cyclic hydrocarbon groups in R ¹⁰⁴ to R ¹⁰⁵ may contain heteroatoms such as heterocycles. Specifically, for example: the lactone-containing cyclic group respectively represented by the aforementioned general formulas (a2-r-1) to (a2-r-7), the aforementioned general formulas (a5-r-1) to ( a5-r-4) -SO ₂ --containing cyclic groups represented separately, other heterocyclic groups represented by the following chemical formulas (r-hr-1) to (r-hr-16), etc.

Substituents in the cyclic groups of R ¹⁰⁴ to R ¹⁰⁵ include, for example, alkyl groups, alkoxy groups, halogen atoms, halogenated alkyl groups, hydroxyl groups, carbonyl groups, and nitro groups. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, most preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. The alkoxy group as a substituent is preferably an alkoxy group with 1 to 5 carbon atoms, such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert -Butoxy is preferred, and methoxy and ethoxy are most preferred. The halogen atom as a substituent includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred. The halogenated alkyl group as a substituent is an alkyl group with 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, tert-butyl, etc., part or all of the hydrogen atoms of the aforementioned halogen Substitution of atoms, etc. The carbonyl group as a substituent is a group substituting a methylene group (-CH ₂ -) constituting a cyclic hydrocarbon group.

Chained alkyl groups which may have substituents: The chained alkyl groups of R ¹⁰⁴ to R ¹⁰⁵ may be linear or branched. The linear alkyl group preferably has 1 to 20 carbons, more preferably 1 to 15 carbons, most preferably 1 to 10 carbons. Specifically, examples include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl base, isotridecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, two Undecyl, behenyl, etc. The branched alkyl group preferably has 3-20 carbons, more preferably 3-15 carbons, most preferably 3-10 carbons. Specifically, examples include: 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, etc.

Chain alkenyl groups that may have substituents: Chain alkenyl groups of R ¹⁰⁴ to R ¹⁰⁵ can be either linear or branched, preferably with 2 to 10 carbons, and the number of carbons is 2-5 is preferable, 2-4 carbon number is more preferable, and 3 carbon number is especially preferable. Straight-chain alkenyl, such as vinyl, propenyl (allyl), butynyl, etc. Examples of branched alkenyl include 1-methylvinyl, 2-methylvinyl, 1-methylacryl, 2-methacryl, and the like. Among the above chain alkenyl groups, straight chain alkenyl groups are preferred, vinyl and propenyl groups are preferred, and vinyl groups are particularly preferred.

The substituents in the chain alkyl or alkenyl groups of R ¹⁰⁴ to R ¹⁰⁵ include, for example, alkoxy groups, halogen atoms, halogenated alkyl groups, hydroxyl groups, carbonyl groups, nitro groups, amino groups, and the above-mentioned R ¹⁰⁴ to R ¹⁰⁵ The ring group and so on.

Among them, R ¹⁰⁴ and R ¹⁰⁵ are preferably chained alkyl groups which may have substituents, and preferably linear or branched chain alkyl groups, or linear or branched chain fluorinated alkyl groups. The chain alkyl group preferably has 1-10 carbon atoms, more preferably 1-7 carbon atoms, and particularly preferably 1-3 carbon atoms. When the carbon numbers of the chained alkyl groups of R ¹⁰⁴ and R ¹⁰⁵ are within the range of the above-mentioned carbon numbers, the smaller the better, for reasons such as good solubility in solvents for resists, etc. In addition, in chain alkyl groups of R ¹⁰⁴ and R ¹⁰⁵ , the more hydrogen atoms substituted by fluorine atoms, the stronger the strength of the acid, which is more preferable. The ratio of fluorine atoms in the chain alkyl group, that is, the fluorination rate, is preferably 70-100%, more preferably 90-100%, most preferably a perfluoroalkyl group in which all hydrogen atoms are replaced by fluorine atoms. In formula (b-2), V ¹⁰² and V ¹⁰³ are each independently a single bond, an alkylene group, or a fluorinated alkylene group, which are the same as V ¹⁰¹ in formula (b-1). In formula (b-2), L ¹⁰¹ and L ¹⁰² are each independently a single bond or an oxygen atom.

・In the anion moiety formula (b-3) of component (b-3), R ¹⁰⁶ to R ¹⁰⁸ are each independently a cyclic group that may have a substituent, a chain alkyl group that may have a substituent, or an optional substituent The chain alkenyl group has the same content as R ¹⁰¹ in formula (b-1). L ¹⁰³ to L ¹⁰⁵ are each independently a single bond, -CO- or -SO ₂ -.

{Cation part} In the formulas (b-1), (b-2) and (b-3), m is an integer of 1 or more, and M' ^m+ is an onium cation with a valence of m, and the cations of perdolium and iodonium are used as As preferred examples, organic cations represented by the following general formulas (ca-1) to (ca-5) are particularly preferred.

[式中，R²⁰¹ ～R²⁰⁷ ，及R²¹¹ ～R²¹² 各別獨立表示可具有取代基之芳基、烷基或烯基；R²⁰¹ ～R²⁰³ 、R²⁰⁶ ～R²⁰⁷ 、R²¹¹ ～R²¹² 可相互鍵結並與式中的硫原子共同形成環；R²⁰⁸ ～R²⁰⁹ 各別獨立表示氫原子或碳數1～5之烷基；R²¹⁰ 為可具有取代基之芳基、可具有取代基之烷基、可具有取代基之烯基，或可具有取代基之含-SO₂ -之環式基；L²⁰¹ 表示-C(=O)-或-C(=O)-O-；Y²⁰¹ 各自獨立表示伸芳基、伸烷基或伸烯基；x為1或2；W²⁰¹ 表示(x+1)價之連結基]。

[In the formula, R ²⁰¹ ~ R ²⁰⁷ , and R ²¹¹ ~ R ²¹² each independently represent an aryl group, an alkyl group or an alkenyl group that may have a substituent; R ²⁰¹ ~ R ²⁰³ , R ²⁰⁶ ~ R ²⁰⁷ , R ²¹¹ ~ R ²¹² can be bonded to each other and form a ring together with the sulfur atom in the formula; R ²⁰⁸ ~ R ²⁰⁹ each independently represent a hydrogen atom or an alkyl group with 1 to 5 carbons; R ²¹⁰ is an aryl group that may have a substituent, may have Alkyl group with substituent, alkenyl group with substituent, or cyclic group containing -SO ₂ - with substituent; L ²⁰¹ represents -C(=O)- or -C(=O)-O- ; Y ²⁰¹ each independently represents an aryl, an alkyl or an alkenyl; x is 1 or 2; W ²⁰¹ represents a linking group of (x+1) valence].

Aryl groups in R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² include, for example, unsubstituted aryl groups having 6 to 20 carbon atoms, and phenyl and naphthyl groups are preferred. The alkyl groups in R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² are preferably chain or cyclic alkyl groups with 1 to 30 carbon atoms. R ²⁰¹ to R ²⁰⁷ and the alkenyl group in R ²¹¹ to R ²¹² preferably have 2 to 10 carbon atoms. The substituents that R ²⁰¹ to R ²⁰⁷ and R ²¹⁰ to R ²¹² may have include, for example, alkyl groups, halogen atoms, halogenated alkyl groups, carbonyl groups, cyano groups, amino groups, aryl groups, and the following formula (ca-r -1)～(ca-r-7) respectively represent the basis, etc.

[式中，R’²⁰¹ 各別獨立為氫原子、可具有取代基之環式基、可具有取代基之鏈狀烷基，或可具有取代基之鏈狀烯基]。

[wherein, ^R'201 are each independently a hydrogen atom, a cyclic group that may have a substituent, a chain alkyl group that may have a substituent, or a chain alkenyl group that may have a substituent].

The cyclic group that may have a substituent, the chain-like alkyl group that may have a substituent, or the chain ^- like alkenyl group that may have a substituent of R'201, except that R in the aforementioned formula (b-1) ¹⁰¹ is the same Other than the contents etc., the cyclic group which may have a substituent or the chain alkyl group which may have a substituent may be the same as the acid dissociative group represented by said formula (a1-r-2), for example.

When R ²⁰¹ ～R ²⁰³ , R ²⁰⁶ ～R ²⁰⁷ , R ²¹¹ ～R ²¹² are bonded to each other and form a ring with the sulfur atom in the formula, they can be interposed by heteroatoms such as sulfur atom, oxygen atom, nitrogen atom, etc. , or carbonyl, -SO-, -SO ₂ -, -SO ₃ -, -COO-, -CONH- or -N(R _N )- (the R _N is an alkyl group with 1 to 5 carbons) and other functions The base is bonded. The formed ring is a ring formed by including a sulfur atom in the ring skeleton in the formula, preferably a 3- to 10-membered ring, particularly preferably a 5- to 7-membered ring, including a sulfur atom. Specific examples of the formed ring, for example: thiophene ring, thiazole ring, benzothiophene ring, thianthrene ring, benzothiophene ring, dibenzothiophene ring, 9H-thioxanthene ring, thioxanthone ring, thianthrene ring , phenanthiazine ring, tetrahydrothiophenium ring, tetrahydrothiopyrylium ring, etc.

R ²⁰⁸ ~ R ²⁰⁹ each independently represent a hydrogen atom or an alkyl group with 1 to 5 carbons, preferably a hydrogen atom or an alkyl group with 1 to 3 carbons. When they are alkyl groups, they can also be bonded to each other to form ring.

R ²¹⁰ is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a cyclic group containing -SO ₂ - which may have a substituent. The aryl group in ^R210 includes, for example, unsubstituted aryl groups having 6 to 20 carbon atoms, and phenyl and naphthyl groups are preferred. The alkyl group in ^R210 is preferably a chain or cyclic alkyl group with 1 to 30 carbon atoms. The alkenyl group in R ²¹⁰ preferably has 2-10 carbon atoms. The -SO ₂ --containing cyclic group that may have substituents in R ²¹⁰ includes, for example, the -SO 2 -containing groups represented by the aforementioned general formulas (a5-r-1) _to (a5-r-4) respectively. The content of the cyclic group of - is the same, among them, the "polycyclic group containing -SO ₂ -" is preferable, and the group represented by the general formula (a5-r-1) is more preferable .

In the aforementioned formula (ca-4) and formula (ca-5), Y ²⁰¹ each independently represents an aryl, an alkylene or an alkenylene. The arylylene group in ^Y201 includes, for example, a group obtained by removing one hydrogen atom from the aryl group exemplified by the aromatic hydrocarbon group in ^R101 in the above formula (b-1). The alkylene group and alkenylene group in ^Y201 include, for example, those obtained by removing one hydrogen atom from the group exemplified by the chain alkyl group and chain alkenyl group of ^R101 in the aforementioned formula (b-1). Base etc.

In the aforementioned formula (ca-4) and formula (ca-5), x is 1 or 2. W ²⁰¹ is (x+1) valence, that is, a divalent or trivalent linking group. The divalent linking group in W ²⁰¹ is preferably a divalent hydrocarbon group that may have a substituent, for example: the same divalent hydrocarbon group that may have a substituent as Ya ²¹ in the above general formula (a2-1) The hydrocarbon group. The divalent linking group in W ²⁰¹ may be linear, branched, or cyclic, and cyclic is preferred. Among them, a group obtained by combining two carbonyl groups at both ends of the aryl group is preferable. The arylylene group includes, for example, a phenylene group, a naphthylene group, etc., and a phenylene group is particularly preferred. The trivalent linking group in W ²⁰¹ includes, for example, the group obtained by removing one hydrogen atom from the divalent linking group in W ²⁰¹ above, and the aforementioned divalent linking group bonded to the aforementioned divalent linking group. And get the foundation and so on. The trivalent linking group in W ²⁰¹ is preferably a group in which an aryl group is bonded to two carbonyl groups.

Preferable cations represented by the aforementioned formula (ca-1) specifically include cations represented by the following formulas (ca-1-1) to (ca-1-72), respectively.

[式中，g1、g2、g3表示重複之數目，g1為1～5之整數，g2為0～20之整數，g3為0～20之整數]。

[wherein, g1, g2, and g3 represent the number of repetitions, g1 is an integer of 1 to 5, g2 is an integer of 0 to 20, and g3 is an integer of 0 to 20].

[式中，R”²⁰¹ 為氫原子或取代基，又，該取代基與前述R²⁰¹ ～R²⁰⁷ ，及R²¹⁰ ～R²¹² 中被列舉作為可具有的取代基之基團為相同之內容]。

[wherein, R" ²⁰¹ is a hydrogen atom or a substituent, and the substituent is the same as the substituents listed as optional substituents in R ²⁰¹ to R ²⁰⁷ and R ²¹⁰ to R ²¹² above] .

Preferable cations represented by the aforementioned formula (ca-2) specifically include diphenyliodonium cations, bis(4-tert-butylphenyl)iodonium cations, and the like.

Preferable cations represented by the aforementioned formula (ca-3) specifically include cations represented by the following formulas (ca-3-1) to (ca-3-6), respectively.

Preferable cations represented by the aforementioned formula (ca-4) specifically include cations represented by the following formulas (ca-4-1) to (ca-4-2), respectively.

In addition, as the cation represented by the above-mentioned formula (ca-5), cations respectively represented by the following general formulas (ca-5-1) to (ca-5-3) can also be used.

Among the above, the cation part [(M' ^m+ ) _{1 / m} ] is preferably the cation represented by the general formula (ca-1), and the formula (ca-1-1)～(ca-1-72) The cations indicated separately are preferred.

In the resist composition of this embodiment, the (B1) component preferably contains the aforementioned (b-1) component; the compound represented by the following general formula (b-1-1) (hereinafter also referred to as "(b-1-1) component"), a compound represented by the following general formula (b-1-2) (hereinafter also referred to as "(b-1-2) component"), the following general formula ( The compound represented by b-1-3) (hereinafter also referred to as "(b-1-3) component"), the compound represented by the following general formula (b-1-4) (hereinafter also referred to as " (b-1-4) Component"), and a compound represented by the following general formula (b-1-5) (hereinafter also referred to as "(b-1-5) Component"). At least one of them is preferred; it is more preferable to contain at least one selected from the group consisting of (b-1-1), (b-1-4) and (b-1-5) .

[式中，R”¹⁰¹ ～R”¹⁰⁴ ，為各別獨立之含有可具有取代基的芳香環之烴基；v”各別獨立為0～3之整數，q”為1～20之整數，t”各別獨立為1～3之整數，n”為0或1]。

[In the formula, R" ¹⁰¹ to R" ¹⁰⁴ are independently hydrocarbon groups containing aromatic rings that may have substituents; v" are each independently an integer of 0 to 3, q" is an integer of 1 to 20, and t " are each independently an integer of 1 to 3, and n" is 0 or 1].

[式中，Rx⁵ ～Rx⁶ 各別獨立表示可具有取代基的烴基或氫原子。

為雙鍵或單鍵。Rz¹ ～Rz⁴ 為各別獨立，且於原子價容許時，表示可具有取代基之烴基或氫原子，或2個以上可相互鍵結形成環結構。其中，Rx⁵ ～Rx⁶ 及Rz¹ ～Rz⁴ 中之至少1個具有下述式(b1-r-an1)所表示之陰離子基，且使陰離子部全體為n價的陰離子。n為1以上之整數。 R⁰²¹ 為烷基、烷氧基、鹵素原子、鹵化烷基、羥基、羰基或硝基。 n1為1～3之整數。n11為0～8之整數。 R⁰²² 為烷基、烷氧基、鹵素原子、鹵化烷基、羥基、羰基或硝基。 n2為1～3之整數。n21為0～8之整數]。

[wherein, Rx ⁵ to Rx ⁶ each independently represent a hydrocarbon group which may have a substituent or a hydrogen atom.

for double or single bonds. Rz ¹ to Rz ⁴ are each independently, and represent a hydrocarbon group or a hydrogen atom which may have a substituent, or two or more of which may be bonded to each other to form a ring structure if the atomic valence permits. Among them, at least one of Rx ⁵ to Rx ⁶ and Rz ¹ to Rz ⁴ has an anion group represented by the following formula (b1-r-an1), and the entire anion portion is an n-valent anion. n is an integer of 1 or more. R ⁰²¹ is an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group or a nitro group. n1 is an integer of 1-3. n11 is an integer of 0-8. R ⁰²² is an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group or a nitro group. n2 is an integer of 1-3. n21 is an integer of 0 to 8].

[式中，R^b01 表示碳數1～5之氟化烷基或氟原子。V^b01 表示伸烷基、氟化伸烷基或單鍵。Y^b01 表示2價之連結基或單鍵]。

[In the formula, R ^b01 represents a fluorinated alkyl group or a fluorine atom having 1 to 5 carbon atoms. V ^b01 represents an alkylene group, a fluorinated alkylene group or a single bond. Y ^b01 represents a divalent linking group or a single bond].

In the aforementioned formulas (b-1-1) to (b-1-4), the hydrocarbon groups containing aromatic rings that may have substituents in R" ¹⁰¹ to R" ¹⁰⁴ are represented by the above-mentioned R ¹⁰¹ , R ¹⁰⁴ and R ¹⁰⁶ The groups exemplified as the hydrocarbon group having an aromatic ring which may have a substituent are preferable. The aforementioned substituents are the same as the substituents that may be substituted for the aromatic rings in R ¹⁰¹ , R ¹⁰⁴ and R ¹⁰⁶ . Among them, R" ¹⁰¹ is preferably an optionally substituted phenyl group or an optionally substituted naphthyl group. Also, R" ¹⁰² is preferably an optionally substituted phenyl group.

In the aforementioned formula (b-1-5), Rx ⁵ to Rx ⁶ each independently represent a hydrocarbon group or a hydrogen atom which may have a substituent. Rz ¹ to Rz ⁴ are each independently, and represent a hydrocarbon group or a hydrogen atom which may have a substituent, or two or more of which may be bonded to each other to form a ring structure if the atomic valence permits. The hydrocarbon groups in Rx ⁵ to Rx ⁶ and Rz ¹ to Rz ⁴ may be aliphatic hydrocarbon groups, aromatic hydrocarbon groups, cyclic hydrocarbon groups, or chain hydrocarbon groups. For example, among Rx ⁵ to Rx ⁶ and Rz ¹ to Rz ⁴ , the hydrocarbon group that may have a substituent includes, for example, a cyclic group that may have a substituent, a chain alkyl group that may have a substituent, or an optionally substituted The chain alkenyl of the base, etc.

Cyclic group which may have a substituent: The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group not having aromaticity. In addition, the aliphatic hydrocarbon group may be saturated or unsaturated, but usually saturated is preferred. Also, the cyclic hydrocarbon groups in Rx ⁵ to Rx ⁶ and Rz ¹ to Rz ⁴ may contain heteroatoms such as heterocyclic rings.

The aromatic hydrocarbon groups in Rx ⁵ to Rx ⁶ and Rz ¹ to Rz ⁴ are hydrocarbon groups having an aromatic ring. The carbon number of the aromatic hydrocarbon group is preferably 3-30, more preferably 5-30, more preferably 5-20, particularly preferably 6-15, and 6-30. 10 is the best. Wherein, the carbon number does not include the carbon number in the substituent. The aromatic rings possessed by the aromatic hydrocarbon groups in Rx ⁵ to Rx ⁶ and Rz ¹ to Rz ⁴ specifically include, for example, benzene, terrene, naphthalene, anthracene, phenanthrene, biphenyl, or the aromatic rings that constitute these aromatic rings. Aromatic heterocycles in which part of the carbon atoms are replaced by heteroatoms, etc. The hetero atom in the aromatic heterocycle includes, for example, an oxygen atom, a sulfur atom, a nitrogen atom, and the like. The aromatic hydrocarbon groups in Rx ⁵ to Rx ⁶ and Rz ¹ to Rz ⁴ specifically include groups obtained by removing one hydrogen atom from the aforementioned aromatic ring (aryl groups: for example: phenyl, naphthalene, etc.) group, etc.), a group obtained by substituting one of the hydrogen atoms of the aforementioned aromatic ring with an alkylene group (for example: benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1 Aralkyl groups such as -naphthylethyl, 2-naphthylethyl, etc.) etc. The carbon number of the aforementioned alkylene group (alkane chain in the aralkyl group) is preferably 1-4, more preferably 1-2, and particularly preferably 1.

The cyclic aliphatic hydrocarbon group in Rx ⁵ to Rx ⁶ and Rz ¹ to Rz ⁴ includes, for example, an aliphatic hydrocarbon group containing a ring in its structure. The aliphatic hydrocarbon group containing a ring in the structure includes, for example: an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), an alicyclic hydrocarbon group bonded to a straight chain or a branched chain A group obtained at the end of an aliphatic hydrocarbon group, a group obtained by interposing an alicyclic hydrocarbon group in the middle of a linear or branched aliphatic hydrocarbon group, etc. The aforementioned alicyclic hydrocarbon group preferably has 3 to 20 carbons, more preferably 3 to 12 carbons. The aforementioned alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocyclic alkane. The monocyclic alkanes preferably have 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycyclic alkane, and the polycyclic alkane preferably has 7 to 30 carbon atoms. Among them, the polycyclic alkanes are: adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc., which have polycyclic skeletons with cross-linked ring systems; A polycyclic alkane having a polycyclic skeleton of a condensed ring system such as a cyclic group of a cholesterol skeleton is preferable.

Among them, the cyclic aliphatic hydrocarbon groups in Rx ⁵ to Rx ⁶ and Rz ¹ to Rz ⁴ are preferably those obtained by removing one or more hydrogen atoms from monocyclic alkanes or polycyclic alkanes. A group obtained by removing one hydrogen atom from monocyclic alkane is preferable, and a group obtained by removing one hydrogen atom from cyclopentane or cyclohexane is particularly preferable.

A straight-chain aliphatic hydrocarbon group that can be bonded to an alicyclic hydrocarbon group, preferably with 1 to 10 carbons, more preferably 1 to 6 carbons, more preferably 1 to 4 carbons, and with 1 to 4 carbons 1 to 3 is the best. Straight-chain aliphatic hydrocarbon groups are preferably straight-chain alkylene groups. Specifically, examples include: methylene [-CH ₂ -], ethylene [-(CH ₂ ) ₂ -], Trimethyl[-(CH ₂ ) ₃ -], Tetramethyl[-(CH ₂ ) ₄ -], Pentamethyl[-(CH ₂ ) ₅ -], etc. A branched aliphatic hydrocarbon group that can be bonded to an alicyclic hydrocarbon group, preferably with 2 to 10 carbons, more preferably 3 to 6 carbons, more preferably 3 or 4 carbons, and 3 carbons for the best. The branched aliphatic hydrocarbon group is preferably a branched chain alkylene group. Specifically, examples include: -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ )(CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ -, etc. ; -CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )-, -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C( CH ₂ CH ₃ ) ₂ -CH ₂ - and other alkyl ethylene groups; -CH(CH ₃ ) CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ ) CH ₂ - and other alkyl trimethyl groups; -CH (CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ -, alkylene such as tetramethylene, alkylene such as tetramethyl, etc. The alkyl group in the alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

In addition, the cyclic groups of Rx ⁵ to Rx ⁶ and Rz ¹ to Rz ⁴ , for example, in -COOR ^XYZ and -OC(=O)R ^XYZ , R ^XYZ is a lactone-containing cyclic group or a carbonate-containing ring A formula group or a ring group containing -SO ₂ -.

The substituents in the cyclic groups of Rx ⁵ to Rx ⁶ and Rz ¹ to Rz ⁴ include, for example, alkyl groups, alkoxy groups, halogen atoms, halogenated alkyl groups, hydroxyl groups, nitro groups, and carbonyl groups. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, most preferably a methyl group, ethyl group, propyl group, n-butyl group, or tert-butyl group. The alkoxy group as a substituent is preferably an alkoxy group with 1 to 5 carbon atoms, such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert -Butoxy is preferred, and methoxy and ethoxy are most preferred. The halogen atom as a substituent includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred. The halogenated alkyl group as a substituent is an alkyl group with 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, tert-butyl, etc., part or all of the hydrogen atoms of the aforementioned halogen Substitution of atoms, etc. The carbonyl group as a substituent is a group substituting a methylene group (-CH ₂ -) constituting a cyclic hydrocarbon group.

Chained alkyl groups which may have substituents: The chained alkyl groups of Rx ⁵ to Rx ⁶ and Rz ¹ to Rz ⁴ may be linear or branched. The linear alkyl group preferably has 1 to 20 carbons, more preferably 1 to 15 carbons, most preferably 1 to 10 carbons. Specifically, examples include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl base, isotridecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, two Undecyl, behenyl, etc. The branched alkyl group preferably has 3-20 carbons, more preferably 3-15 carbons, most preferably 3-10 carbons. Specifically, examples include: 1-methylethyl, 1,1-dimethylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methyl Butyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl Base etc.

Chain alkenyl groups that may have substituents: Chain alkenyl groups of Rx ⁵ ~ Rx ⁶ , Rz ¹ ~ Rz ⁴ can be either straight chain or branched chain, and the carbon number is 2 ~ Preferably 10, more preferably 2-5 carbons, more preferably 2-4 carbons, particularly preferably 3 carbons. Straight-chain alkenyl, such as vinyl, propenyl (allyl), butynyl, etc. Examples of branched alkenyl include 1-methylvinyl, 2-methylvinyl, 1-methylacryl, 2-methacryl, and the like. Among the above chain alkenyl groups, straight chain alkenyl groups are preferred, vinyl and propenyl groups are preferred, and vinyl groups are particularly preferred.

The substituents in the chain alkyl or alkenyl of Rx ⁵ ~ Rx ⁶ , Rz ¹ ~ Rz ⁴ include, for example: alkoxy, halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), halogenated Alkyl group, hydroxyl group, carbonyl group, nitro group, amino group, cyclic group among Rx ⁵ to Rx ⁶ , Rz ¹ to Rz ⁴ mentioned above, etc.

The hydrocarbon groups in Rx ⁵ to Rx ⁶ and Rz ¹ to Rz ⁴ are preferably cyclic groups which may have substituents or chain alkyl groups which may have substituents among the above hydrocarbon groups.

In the aforementioned formula (b-1-5), two or more of Rz ¹ to Rz ⁴ may be bonded to each other to form a ring structure. For example, Rz ¹ may form a ring structure with any of Rz ² to Rz ⁴ . Specifically, for example, one side of the six-membered ring in the common formula (b-1-5) (formed by the carbon atom bonded to Rz ¹ and Rz ² , and the carbon atom bonded to Rz ³ and Rz ⁴ The ring structure of the bond), the ring structure formed by the bond of Rz ¹ and Rz ² , the ring structure formed by the bond of Rz ³ and Rz ⁴ , etc. Among these Rz ¹ to Rz ⁴ , the ring structure formed of two or more may be an alicyclic hydrocarbon or an aromatic hydrocarbon, and an aromatic hydrocarbon is particularly preferable. In addition, the ring structure may be a polycyclic structure formed of ring structures other than these.

The alicyclic hydrocarbon formed from two or more of Rz ¹ to Rz ⁴ may be polycyclic or monocyclic. Monocyclic alicyclic hydrocarbons are preferably monocyclic alkanes. The monocyclic alkanes preferably have 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. Polycyclic alicyclic hydrocarbons are preferably polycyclic alkanes. The polycyclic alkanes are preferably those with 7 to 30 carbon atoms. Specifically, those with cross-linked ring systems such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. Polycyclic alkanes with a polycyclic skeleton; polycyclic alkanes with a polycyclic skeleton having a condensed ring system such as a cyclic group having a cholesterol skeleton are preferred. It can also be a heterocyclic structure in which part of the carbon atoms are replaced by heteroatoms, and nitrogen-containing heterocyclic rings are particularly preferred, specifically, for example: cyclic imides and the like.

Aromatic hydrocarbons formed by two or more of Rz ¹ to Rz ⁴ , such as: benzene, terrene, naphthalene, anthracene, phenanthrene, biphenyl, or some of the carbon atoms constituting these aromatic rings are heterogeneous Aromatic heterocycles obtained by atom substitution, etc.

The ring structure (alicyclic hydrocarbon, aromatic hydrocarbon) formed by Rz ¹ to Rz ⁴ may have a substituent. The substituents here are, for example: the substituents in the cyclic groups of Rx ¹ ~ Rx ⁴ , Ry ¹ ~ Ry ² , Rz ¹ ~ Rz ⁴ mentioned above (such as: alkyl, alkoxy, halogen atom, halogenated alkyl group, hydroxyl group, nitro group, carbonyl group, etc.) are the same content, etc.

A ring structure formed by two or more of Rz ¹ to Rz ⁴ , wherein, from the viewpoint of controlling the diffusion of acid generated by exposure, one side of the six-membered ring in the common formula (b-1-5) ( The carbon atoms to which Rz ¹ and Rz ² are bonded, and the carbon atoms to which Rz ³ and Rz ⁴ are bonded) ring structures are preferred, and aromatic ring structures are more preferred.

In addition, in the aforementioned formula (b-1-5), "when the atomic valence is allowed" means the following. That is, when the carbon atoms to which Rz ¹ and Rz ² are bonded, and the carbon atoms to which Rz ³ and Rz ⁴ are bonded are single bonds, all Rz ¹ , Rz ² , Rz ³ , and Rz ⁴ exist. When the carbon atom bonded to Rz ¹ and Rz ² is double bonded to the carbon atom bonded to Rz ³ and Rz ⁴ , only one of Rz ¹ or Rz ² exists, and only one of Rz ³ and Rz ⁴ exists One exists. Also, for example, when Rz ¹ and Rz ³ are bonded to form an aromatic ring structure, neither Rz ² nor Rz ⁴ exists.

In the aforementioned formula (b-1-5), R ⁰²¹ is an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group or a nitro group. The alkyl group in R ⁰²¹ is preferably an alkyl group with 1 to 5 carbon atoms, especially methyl, ethyl, propyl, n-butyl, and tert-butyl. The alkoxy group in R ⁰²¹ is preferably an alkoxy group with 1 to 5 carbon atoms, such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert- Butoxy is preferred, and methoxy and ethoxy are most preferred. The halogen atom in R ⁰²¹ includes, for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc., and fluorine atom is preferred. The halogenated alkyl group in R ⁰²¹ is an alkyl group with 1 to 5 carbon atoms, such as a part or all of the hydrogen atoms in methyl, ethyl, propyl, n-butyl, tert-butyl, etc. A group obtained by substituting a halogen atom, etc.

In the aforementioned formula (b-1-5), n1 is an integer of 1 to 3, preferably 1 or 2, particularly preferably 1. In the aforementioned formula (b-1-5), n11 is an integer of 0-8, preferably an integer of 0-4, more preferably 0, 1 or 2, particularly preferably 0 or 1.

In the aforementioned formula (b-1-5), R ⁰²² is an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, or a nitro group, and the contents are the same as those of the aforementioned R ⁰²¹ . In the aforementioned formula (b-1-5), n2 is an integer of 1 to 3, preferably 1 or 2, particularly preferably 1. In the aforementioned formula (b-1-5), n21 is an integer of 0-8, preferably an integer of 0-4, more preferably 0, 1 or 2, particularly preferably 0 or 1.

Wherein, in the aforementioned formula (b-1-5), at least one of Rx ⁵ to Rx ⁶ and Rz ¹ to Rz ⁴ has an anionic group represented by the aforementioned formula (b1-r-an1), and the anionic part All are n-valent anions. n is an integer of 1 or more.

In the aforementioned formula (b1-r-an1), R ^b01 represents a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. R ^b01 is preferably a perfluoroalkyl group having 1 to 5 carbon atoms or a fluorine atom, more preferably a fluorine atom.

In the aforementioned formula (b1-r-an1), V ^b01 represents an alkylene group, a fluorinated alkylene group, or a single bond. The alkylene group and fluorinated alkylene group in V ^b01 preferably have 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms. The fluorinated alkylene group in V ^b01 is a group obtained by substituting part or all of the hydrogen atoms of the alkylene group with fluorine atoms, etc. Among them, V ^b01 is preferably an alkylene group having 1 to 4 carbons, a fluorinated alkylene group having 1 to 4 carbons, or a single bond.

In the aforementioned formula (b1-r-an1), Y ^b01 represents a divalent linking group or a single bond. The divalent linking group in Y ^b01 is preferably exemplified by a divalent linking group containing an oxygen atom. When Y ^b01 is a divalent linking group containing an oxygen atom, this Y ^b01 may contain atoms other than an oxygen atom. Atoms other than oxygen atoms, such as carbon atoms, hydrogen atoms, sulfur atoms, nitrogen atoms, etc. Divalent linking groups containing oxygen atoms, such as: oxygen atom (ether bond: -O-), ester bond (-C(=O)-O-), oxycarbonyl (-OC(=O) -), amide bond (-C(=O)-NH-), carbonyl (-C(=O)-), carbonate bond (-OC(=O)-O-) and other non-hydrocarbon systems A linking group containing an oxygen atom; a combination of the non-hydrocarbon-based linking group containing an oxygen atom and an alkylene group, etc. In this combination, a sulfonyl group (-SO ₂ -) may be further bonded. Examples of the divalent linking group containing an oxygen atom include linking groups represented by the aforementioned general formulas (y-al-1) to (y-al-9), respectively.

Y ^b01 is preferably a divalent linking group containing an ester bond, or a divalent linking group containing an ether bond, represented by the aforementioned formulas (y-al-1) to (y-al-6) respectively A linker is preferred.

Specific examples of the anionic group represented by the aforementioned formula (b1-r-an1) include: When Y ^b01 is a single bond, for example: -CH ₂ CF ₂ SO ₃ ^- , -CF ₂ CF ₂ SO ₃ ^- , - Fluorinated alkylsulfonate anion such as fluoromethanesulfonate anion or perfluorobutanesulfonate anion. When Y ^b01 is a divalent linking group containing an oxygen atom, it is, for example, an anion represented by any one of the following formulas (b1-r-an11) to (b1-r-an13).

[式中，V”¹⁰¹ 為單鍵、碳數1～4之伸烷基，或碳數1～4之氟化伸烷基。R¹⁰² 為氟原子或碳數1～5之氟化烷基。v”各別獨立為0～3之整數。q”各別獨立為1～20之整數。n”為0或1]。

[In the formula, V" ¹⁰¹ is a single bond, an alkylene group with 1 to 4 carbons, or a fluorinated alkylene group with 1 to 4 carbons. R ¹⁰² is a fluorine atom or a fluorinated alkyl group with 1 to 5 carbons .v" are each independently an integer of 0-3. q" are each independently an integer of 1 to 20. n" is 0 or 1].

In the aforementioned formulas (b1-r-an11) to (b1-r-an13), V" ¹⁰¹ is a single bond, an alkylene group with 1 to 4 carbons, or a fluorinated alkylene group with 1 to 4 carbons. V " ¹⁰¹ is preferably a single bond, an alkylene group (methylene) with 1 carbon, or a fluorinated alkylene group with 1 to 3 carbons.

In the aforementioned formulas (b1-r-an11) to (b1-r-an13), R ¹⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbons. R ¹⁰² is preferably a perfluoroalkyl group having 1 to 5 carbon atoms or a fluorine atom, more preferably a fluorine atom.

In the aforementioned formulas (b1-r-an11) to (b1-r-an13), v" is an integer of 0-3, preferably 0 or 1. q" is an integer of 1-20, preferably an integer of 1-10, more preferably an integer of 1-5, more preferably 1, 2 or 3, particularly preferably 1 or 2. n" is 0 or 1, preferably 0.

(b-1-5) The number of anionic groups in the component may be 1 or 2 or more, preferably 1. The component (b-1-5) is an anion that makes the entire anion portion an n-valent anion. n is an integer of 1 or more, preferably 1 or 2, more preferably 1.

Specific examples of preferred compounds of the component (B1) are listed below, for example.

In the resist composition of this embodiment, (B1) component may be used individually by 1 type, and may use 2 or more types together. In the resist composition of this embodiment, the content of component (B1) is preferably 0.1 to 100 parts by mass, more preferably 0.5 to 80 parts by mass, and 1 to 60 parts by mass relative to 100 parts by mass of component (A). The quality part is better. (B1) When the content of the component is above the lower limit of the above-mentioned preferred range, it can improve the sensitivity, resolution performance, reduce LWR (Line Wise Roughness), shape and other lithographic etching characteristics in the formation of resist patterns . On the other hand, when it is below the upper limit of the preferable range, it is easier to suppress the film loss of the resist pattern.

・(B2) Components The resist composition of this embodiment may contain an acid generator component (hereinafter, also referred to as "(B2) component") other than the component (B1) within the range that does not impair the effect of the present invention. The component (B2) is not particularly limited, and it can be an acid generator proposed so far as a chemically amplified resist composition. These acid generators include, for example: onium salt-based acid generators such as odonium salts or permeic acid salts, oxime sulfonate-based acid generators; dialkyl or bisarylsulfonyl diazomethanes, poly( Diazomethane-based acid generators such as bissulfonyl) diazomethanes; nitrobenzylsulfonate-based acid generators, iminosulfonate-based acid generators, diazomethane-based acid generators, etc. ingredients.

Onium salt-based acid generators, for example: compounds represented by the following general formula (b-1') (hereinafter also referred to as "(b-1') component"), represented by general formula (b-2') (hereinafter also referred to as "component (b-2')") or a compound represented by the general formula (b-3') (hereinafter also referred to as "component (b-3')"). In addition, the components (b-1'), (b-2') and (b-3') do not contain a compound corresponding to the above-mentioned (B1) component.

[式中，R³⁰¹ 、R³⁰⁴ ～R³⁰⁸ 各別獨立為可具有取代基之環式基、可具有取代基之鏈狀烷基，或可具有取代基之鏈狀烯基。R³⁰⁴ 、R³⁰⁵ 可相互鍵結而形成環。 R³⁰² 為氟原子或碳數1～5之氟化烷基。Y³⁰¹ 為單鍵或含有氧原子的2價之連結基。V³⁰¹ ～V³⁰³ 各別獨立為單鍵、伸烷基或氟化伸烷基。L³⁰¹ ～L³⁰² 各別獨立為單鍵或氧原子。L³⁰³ ～L³⁰⁵ 各別獨立為單鍵、-CO-或-SO₂ -。m為1以上之整數，且M’^m+ 為m價之鎓陽離子]。

[In the formula, R ³⁰¹ , R ³⁰⁴ to R ³⁰⁸ are each independently a cyclic group that may have a substituent, a chain alkyl group that may have a substituent, or a chain alkenyl group that may have a substituent. R ³⁰⁴ and R ³⁰⁵ may be bonded to each other to form a ring. ^R302 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbons. ^Y301 is a single bond or a divalent linking group containing an oxygen atom. V ³⁰¹ to V ³⁰³ are each independently a single bond, an alkylene group or a fluorinated alkylene group. L ³⁰¹ to L ³⁰² are each independently a single bond or an oxygen atom. L ³⁰³ to L ³⁰⁵ are each independently a single bond, -CO- or -SO ₂ -. m is an integer of 1 or more, and M' ^m+ is an m-valent onium cation].

{Anion part} ・In the anion part of the component (b-1'), in the formula (b-1'), R ³⁰¹ is a cyclic group that may have a substituent, a chain alkyl group that may have a substituent, or an optional substituent The chain alkenyl group of the group, the cyclic group that may have substituents, the chain group that may have substituents of R ¹⁰⁵ , R ¹⁰⁷ and R ¹⁰⁸ in the aforementioned formula (b-2) and the aforementioned formula (b-3) The same applies to an alkyl group or a chain alkenyl group which may have a substituent.

The substituents in the chain alkyl or alkenyl of R ³⁰¹ include, for example, alkoxy groups, halogen atoms, halogenated alkyl groups, hydroxyl groups, carbonyl groups, amino groups, and cyclic groups in the above-mentioned R ¹⁰¹ .

Among the above, R ³⁰¹ is preferably a cyclic group that may have a substituent, more preferably a cyclic hydrocarbon group that may have a substituent. More specifically, the base obtained by removing one or more hydrogen atoms from phenyl, naphthyl, and polycyclic alkanes; the aforementioned general formulas (a2-r-1), (a2-r-3)～(a2 -r-7) respectively represent lactone-containing cyclic groups; the aforementioned general formulas (a5-r-1) ~ (a5-r-4) respectively represent -SO ₂ -containing cyclic groups, etc. good.

In formula (b-1'), Y ³⁰¹ is a single bond or a divalent linking group containing an oxygen atom. The divalent linking group containing an oxygen atom in Y ³⁰¹ is the same as the divalent linking group containing an oxygen atom in Y ¹⁰¹ in the aforementioned formula (b-1). Y ³⁰¹ is preferably a divalent linking group containing an ester bond, or a divalent linking group containing an ether bond, represented by the aforementioned general formulas (y-al-1) to (y-al-5) respectively The link base is better.

In the formula (b-1'), V ³⁰¹ is a single bond, an alkylene group or a fluorinated alkylene group. The alkylene group and fluorinated alkylene group in ^V301 are the same as the alkylene group and fluorinated alkylene group in ^V101 in the aforementioned formula (b-1).

In formula (b-1'), R ³⁰² is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbons. R ³⁰² is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom.

Specific examples of the anion part of the component (b-1'), for example: when ^Y301 is a single bond, fluorinated alkyl sulfonate such as trifluoromethanesulfonate anion or perfluorobutanesulfonate anion, etc. Ester anion; When Y ³⁰¹ is a divalent linking group containing an oxygen atom, examples thereof include anions represented by any one of the following formulas (an-1) to (an-3).

[式中，R”³⁰¹ 為可具有取代基之脂肪族環式基、前述式(r-hr-1)～(r-hr-6)所各別表示之基，或可具有取代基之鏈狀烷基；R”³⁰² 為可具有取代基之脂肪族環式基、前述通式(a2-r-1)、(a2-r-3)～(a2-r-7)各別表示之含內酯之環式基，或前述通式(a5-r-1)～(a5-r-4)各別表示之含-SO₂ -之環式基；R”³⁰³ 為可具有取代基芳香族環式基、可具有取代基之脂肪族環式基，或可具有取代基之鏈狀烯基；v”各別獨立為0～3之整數，q”各別獨立為1～20之整數，t”為1～3之整數，n”為0或1]。

[In the formula, R" ³⁰¹ is an aliphatic cyclic group that may have a substituent, a group represented by each of the aforementioned formulas (r-hr-1) to (r-hr-6), or a chain that may have a substituent R" ³⁰² is an aliphatic cyclic group that may have substituents, and the above-mentioned general formulas (a2-r-1), (a2-r-3) ~ (a2-r-7) respectively represent the containing A cyclic group of a lactone, or a cyclic group containing -SO ₂ - represented by the aforementioned general formulas (a5-r-1)~(a5-r-4); R" ³⁰³ is an aromatic group that may have substituents A cyclic group, an aliphatic cyclic group that may have a substituent, or a chain alkenyl group that may have a substituent; v" is each independently an integer of 0 to 3, and q" is each independently an integer of 1 to 20, t" is an integer from 1 to 3, and n" is 0 or 1].

R" ³⁰¹ , R" ³⁰² and R" ³⁰³ may have substituent aliphatic ring group, in the above-mentioned formula (b-2) and the above-mentioned formula (b-3) in R ¹⁰⁵ , R ¹⁰⁷ and R ¹⁰⁸ The group exemplified as a cycloaliphatic hydrocarbon group is preferable. The above-mentioned substituent, and the cycloaliphatic in R ¹⁰⁵ , R ¹⁰⁷ and R ¹⁰⁸ in the above-mentioned formula (b-2) and the above-mentioned formula (b-3) can be substituted The substituents of the hydrocarbon group have the same content and so on.

The aromatic ring group that may have a substituent in R" ³⁰³ is exemplified as the cyclic hydrocarbon group in the aforementioned formula (b-2) and R ¹⁰⁵ , R ¹⁰⁷ , and R ¹⁰⁸ in the aforementioned formula (b-3). The base of the aromatic hydrocarbon group is preferred. The aforementioned substituent, and the substituent that can replace the aforementioned aromatic hydrocarbon group in R ¹⁰⁵ , R ¹⁰⁷ and R ¹⁰⁸ in the aforementioned formula (b-2) and the aforementioned formula (b-3) are same content etc.

The chain-like alkyl group which may have a substituent in R" ³⁰¹ is exemplified as the chain-like alkyl group in the aforementioned formula (b-2) and the aforementioned formula (b-3) in R ¹⁰⁵ , R ¹⁰⁷ and R ¹⁰⁸ The chain alkenyl group which may have a substituent in R" ³⁰³ is exemplified as a chain in R ¹⁰⁵ , R ¹⁰⁷ and R ¹⁰⁸ in the aforementioned formula (b-2) and the aforementioned formula (b-3). The base of alkenyl is preferred.

・In the anion moiety formula (b-2') of component (b-2'), R ³⁰⁴ and R ³⁰⁵ are each independently a cyclic group that may have a substituent, a chain alkyl group that may have a substituent, or may have The chain alkenyl group of the substituent, which is respectively the cyclic group that may have a substituent in R ¹⁰⁵ , R ¹⁰⁷ and R ¹⁰⁸ in the aforementioned formula (b-2) and the aforementioned formula (b-3), may have a substituent The chain alkyl group, or the chain alkenyl group which may have a substituent are the same. However, R ³⁰⁴ and R ³⁰⁵ may be bonded to each other to form a ring. R ³⁰⁴ and R ³⁰⁵ are preferably chained alkyl groups which may have substituents, more preferably linear or branched chain alkyl groups, or linear or branched chain fluorinated alkyl groups. The chain alkyl group preferably has 1-10 carbon atoms, more preferably 1-7 carbon atoms, and particularly preferably 1-3 carbon atoms. When the carbon numbers of the chained alkyl groups of R ³⁰⁴ and R ³⁰⁵ are within the range of the above-mentioned carbon numbers, the smaller the better, for reasons such as good solubility in solvents for resists, etc. Also, in the chain alkyl groups of R ³⁰⁴ and R ³⁰⁵ , the more hydrogen atoms substituted by fluorine atoms, the stronger the strength of the acid, which is more preferable. The ratio of fluorine atoms in the chain alkyl group, that is, the fluorination rate, is preferably 70-100%, more preferably 90-100%, most preferably a perfluoroalkyl group in which all hydrogen atoms are replaced by fluorine atoms. In formula (b-2'), V ³⁰² and V ³⁰³ are each independently a single bond, an alkylene group, or a fluorinated alkylene group, which are the same as V ¹⁰¹ in formula (b-1), etc. . In formula (b-2'), L ³⁰¹ and L ³⁰² are each independently a single bond or an oxygen atom.

・In the anion moiety formula (b-3') of component (b-3'), R ³⁰⁶ to R ³⁰⁸ are each independently a cyclic group that may have a substituent, a chain alkyl group that may have a substituent, or may have a substituent The chain alkenyl group of the substituent, which is respectively the cyclic group that may have a substituent in R ¹⁰⁵ , R ¹⁰⁷ and R ¹⁰⁸ in the aforementioned formula (b-2) and the aforementioned formula (b-3), may have a substituent The chain alkyl group, or the chain alkenyl group which may have a substituent are the same. L ³⁰³ to L ³⁰⁵ are each independently a single bond, -CO- or -SO ₂ -.

{Cation part} In the formulas (b-1'), (b-2') and (b-3'), m is an integer of 1 or more, and M' ^m+ is an onium cation with a valence of m. Odonium cation is a preferable example, for example, organic cations respectively represented by the above-mentioned general formulas (ca-1) to (ca-5).

Preferable cations represented by the above formula (ca-1) specifically include cations represented by the above formulas (ca-1-1) to (ca-1-72), respectively.

Specific examples of preferable cations represented by the above formula (ca-2) include diphenyliodonium cations, bis(4-tert-butylphenyl)iodonium cations, and the like.

Preferable cations represented by the above formula (ca-3) specifically include cations represented by the above formulas (ca-3-1) to (ca-3-6), respectively.

Preferable cations represented by the above formula (ca-4) specifically include cations represented by the above formulas (ca-4-1) to (ca-4-2), respectively.

Preferable cations represented by the above formula (ca-5) specifically include cations represented by the above formulas (ca-5-1) to (ca-5-3), and the like.

Among the above, the cation part [(M' ^m+ ) _{1 / m} ] is preferably the cation represented by the general formula (ca-1), and the formula (ca-1-1)～(ca-1-72) The cations indicated separately are preferred.

In the resist composition of this embodiment, (B2) component may be used individually by 1 type, and may use it in combination of 2 or more types. When the resist composition contains component (B2), the content of component (B2) in the resist composition is preferably less than 50 parts by mass, more preferably 1 to 40 parts by mass, relative to 100 parts by mass of component (A) Good, more preferably 5-30 parts by mass. When the content of the component (B2) is within the above range, sufficient effects can be achieved when the component (B2) is contained, and various lithographic etching properties can be improved.

＜Other ingredients＞ The resist composition of this embodiment may further contain other components other than the above-mentioned (A) component and (B) component. Other components, such as (D) component, (E) component, (F) component, (S) component etc. shown below.

≪Acid diffusion control agent component (D)≫ In the resist composition of this embodiment, in addition to (A) component, or (A) component and (B) component, an acid diffusion control agent component (hereinafter, also referred to as "(D) component") may be contained . Component (D) has an inhibitor (acid diffusion control agent) function of trapping acid generated by exposure in the resist composition. Component (D) may be a photodisintegrating base (D1) (hereinafter, also referred to as "component (D1)") that is decomposed by exposure and loses acid diffusion controllability. A nitrogen organic compound (D2) (hereinafter also referred to as "(D2) component") may also be used.

・(D1) Component The resist composition containing the component (D1) can improve the contrast between the exposed part and the unexposed part of the resist film when the resist pattern is formed. The component (D1) is not particularly limited as long as it is a component decomposed by exposure to lose acid diffusion controllability, and a compound represented by the following general formula (d1-1) (hereinafter also referred to as "(d1-1) component"), a compound represented by the following general formula (d1-2) (hereinafter also referred to as "(d1-2) component"), and a compound represented by the following general formula (d1-3) One or more compounds selected from the group consisting of compounds (hereinafter, also referred to as "(d1-3) component") are preferred. The components (d1-1) to (d1-3) do not act as inhibitors for the loss of acid diffusion control (alkalinity) due to decomposition in the exposed part of the resist film, but have an inhibitory effect in the unexposed part function as an inhibitor.

[式中，Rd¹ ～Rd⁴ 為可具有取代基之環式基、可具有取代基之鏈狀烷基，或可具有取代基之鏈狀烯基。其中，式(d1-2)中之Rd² 中，S原子鄰接的碳原子為不鍵結氟原子者。Yd¹ 為單鍵或2價之連結基；m為1以上之整數，且M^m+ 各別獨立為m價之有機陽離子]。

[In the formula, Rd ¹ to Rd ⁴ are a cyclic group that may have a substituent, a chain alkyl group that may have a substituent, or a chain alkenyl group that may have a substituent. Among them, in Rd ² in the formula (d1-2), the carbon atom adjacent to the S atom is not bonded to a fluorine atom. Yd ¹ is a single bond or a divalent linking group; m is an integer of 1 or more, and M ^m+ are each independently an m-valent organic cation].

{(d1-1) component} ・・In the anion part formula (d1-1), Rd ¹ is a cyclic group that may have a substituent, a chain alkyl group that may have a substituent, or a chain group that may have a substituent Alkenyl, which are respectively the same as R ¹⁰¹ in the aforementioned formula (b-1), etc. Among them, Rd ¹ is preferably an aromatic hydrocarbon group which may have a substituent, an aliphatic ring group which may have a substituent, or a chain alkyl group which may have a substituent. The substituents that these groups may have include, for example: hydroxyl group, side oxygen (oxo) group, alkyl group, aryl group, fluorine atom, fluorinated alkyl group, the above-mentioned general formula (a2-r-1)～( a2-r-7) Each represents a lactone-containing cyclic group, an ether linkage, an ester linkage, or a combination thereof. When containing an ether bond or an ester bond as a substituent, an alkylene group may be interposed in the chain, and the substituent in this case is represented by each of the above formulas (y-al-1) to (y-al-5). It is better not to express the link base. The aforementioned aromatic hydrocarbon group is preferably phenyl or naphthyl. The aforementioned aliphatic cyclic group is preferably a group obtained by removing one or more hydrogen atoms from polycyclic alkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. . The aforementioned chain-like alkyl group preferably has 1 to 10 carbon atoms, specifically, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl , decyl and other linear alkyl groups; 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methyl Branched chains of butyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, etc. The alkyl group, etc.

When the aforementioned chained alkyl group is a fluorinated alkyl group having a fluorine atom as a substituent or a fluorinated alkyl group, the carbon number of the fluorinated alkyl group is preferably 1 to 11, and more preferably 1 to 8 carbons. , with 1 to 4 carbon atoms being more preferred. The fluorinated alkyl group may contain atoms other than fluorine atoms. Atoms other than fluorine atoms, such as oxygen atoms, sulfur atoms, nitrogen atoms, etc. Rd ¹ is preferably a fluorinated alkyl group in which part or all of the hydrogen atoms constituting a straight-chain alkyl group are replaced by fluorine atoms, and all the hydrogen atoms constituting a straight-chain alkyl group are replaced by fluorine atoms The obtained fluorinated alkyl group (linear perfluoroalkyl group) is particularly preferred.

The following are preferable specific examples of the anion portion of the component (d1-1).

・・In the cationic formula (d1-1), M ^m+ is an m-valent organic cation. The organic cations of M ^m+ are preferably exemplified with the same content as the cations respectively represented by the aforementioned general formulas (ca-1) to (ca-5), and those represented by the aforementioned general formula (ca-1) A cation is preferable, and a cation represented by each of the aforementioned formulas (ca-1-1) to (ca-1-72) is more preferable. The component (d1-1) may be used alone or in combination of two or more.

{(d1-2) component} ・・In the anion moiety formula (d1-2), Rd ² is a cyclic group that may have a substituent, a chain alkyl group that may have a substituent, or a chain-like group that may have a substituent Examples of the alkenyl group include the same content as R ¹⁰¹ in the aforementioned formula (b-1), and the like. However, in Rd ² , the carbon atom adjacent to the S atom is not bonded to a fluorine atom (not substituted by fluorine). In this way, the anion of the (d1-2) component can be formed into an anion with a moderately weak acid, and the inhibitory ability as the (D) component can be improved. Rd ² is preferably a chain alkyl group which may have a substituent, or an aliphatic ring group which may have a substituent. The chain alkyl group preferably has 1-10 carbon atoms, more preferably 3-10 carbon atoms. Aliphatic cyclic groups are those obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. (may have substituents); A group obtained by removing one or more hydrogen atoms such as camphor is preferable. The hydrocarbon group of Rd ² may have a substituent ^, and the substituent, for example, may have The substituents are the same content and so on.

The following are preferable specific examples of the anion part of the (d1-2) component.

・・In the cationic formula (d1-2), M ^m+ is an m-valent organic cation, which is the same as M ^m+ in the aforementioned formula (d1-1). (d1-2) component may be used individually by 1 type, and may use it in combination of 2 or more types.

{(d1-3) component} ・・In the anion moiety formula (d1-3), Rd ³ is a cyclic group that may have a substituent, a chain alkyl group that may have a substituent, or a chain-like group that may have a substituent The alkenyl group includes, for example, the same content as R ¹⁰¹ in the aforementioned formula (b-1), etc., and is preferably a cyclic group containing a fluorine atom, a chained alkyl group, or a chained alkenyl group. Among them, the fluorinated alkyl group is preferred, and the same content as the aforementioned fluorinated alkyl group of Rd ¹ is preferred.

In the formula (d1-3), Rd ⁴ is a cyclic group that may have a substituent, a chain alkyl group that may have a substituent, or a chain alkenyl group that may have a substituent, such as: and the aforementioned formula (b R ¹⁰¹ in -1) has the same content and so on. Among them, an alkyl group, an alkoxy group, an alkenyl group, and a cyclic group which may have a substituent are preferable. The alkyl group in Rd ⁴ is preferably a straight-chain or branched-chain alkyl group with 1 to 5 carbon atoms, specifically, methyl, ethyl, propyl, isopropyl, n- Butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. Part of hydrogen atoms in the alkyl group of Rd ⁴ may be substituted by hydroxyl, cyano, etc. The alkoxy group in Rd ⁴ is preferably an alkoxy group with 1 to 5 carbons, specifically, alkoxy groups with 1 to 5 carbons, such as: methoxy, ethoxy, n-propane Oxy, iso-propoxy, n-butoxy, tert-butoxy, etc. Among them, methoxy and ethoxy are preferred.

The alkenyl in Rd ⁴ can be enumerated such as: the same content as R ¹⁰¹ in the above-mentioned formula (b-1), and vinyl, propenyl (allyl), 1-methacryl, 2- Methacryl is preferred. When these groups have a substituent, they may have an alkyl group having 1 to 5 carbons or a halogenated alkyl group having 1 to 5 carbons.

The cyclic group in Rd ⁴ can be enumerated such as: the same content as R ¹⁰¹ in the above-mentioned formula (b-1), wherein it is composed of cyclopentane, cyclohexane, adamantane, norbornane, and isocamphene Alicyclic groups obtained by removing one or more hydrogen atoms from cycloalkanes such as alkane, tricyclodecane, and tetracyclododecane, or aromatic groups such as phenyl and naphthyl are preferred.

In the formula (d1-3), Yd ¹ is a single bond or a divalent linking group. The divalent linking group in ^Yd1 is not particularly limited, and examples thereof include divalent hydrocarbon groups (aliphatic hydrocarbon groups, aromatic hydrocarbon groups) that may have substituents, divalent linking groups containing heteroatoms, etc. . These are the same as the bivalent hydrocarbon group that may have a substituent and the divalent linking group containing a heteroatom listed in the description of the bivalent linking group in Ya ²¹ in the above formula (a2-1), respectively. content etc. Yd ¹ is preferably a carbonyl group, an ester bond, an amide bond, an alkylene group or a combination thereof. The alkylene group is preferably a linear or branched chain alkylene group, more preferably a methylene group or an ethylene group.

The following are preferable specific examples of the anion part of the (d1-3) component.

・・In the cation part formula (d1-3), M ^m+ is an m-valent organic cation, which is the same as M ^m+ in the aforementioned formula (d1-1). The components (d1-3) may be used alone or in combination of two or more.

(D1) As a component, only any one of the said (d1-1)-(d1-3) components may be used, or 2 or more types may be used in combination. When the resist composition contains component (D1), the content of component (D1) is preferably 0.01-50 parts by mass, more preferably 0.05-40 parts by mass, and 0.1-40 parts by mass relative to 100 parts by mass of component (A). 30 parts by mass is better. When the content of the component (D1) is more than the lower limit of the above-mentioned preferable range, it is easy to obtain good lithographic etching characteristics and resist pattern shape. On the other hand, when the content of the component (D1) is below the upper limit of the above-mentioned preferred range, a balance with other components can be achieved, and various favorable lithographic etching properties can be easily formed.

(D1) Manufacturing method of ingredients: There is no particular limitation on the production method of the above-mentioned (d1-1) component and (d1-2) component, which can be produced according to known methods. Also, the method for producing the component (d1-3) is not particularly limited, for example, it can be produced by the same method as described in US2012-0149916.

・The component (D2) of the acid diffusion control agent may contain a nitrogen-containing organic compound component (hereinafter also referred to as "(D2) component") that does not correspond to the above-mentioned component (D1). The component (D2) is not particularly limited as long as it functions as an acid diffusion control agent and does not correspond to the component (D1), and any known component can be used. Among them, aliphatic amines are preferred, and among them, secondary aliphatic amines or tertiary aliphatic amines are particularly preferred. The aliphatic amine is an amine having one or more aliphatic groups, and the aliphatic groups preferably have 1 to 12 carbon atoms. Aliphatic amines include, for example, at least one hydrogen atom in ammonia NH ₃ , amines (alkylamines or alkanolamines) or cyclic amines substituted by alkyl or hydroxyalkyl groups with 12 or less carbon atoms. Specific examples of alkylamines and alkanolamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; diethylamine, di- Dialkylamines such as n-propylamine, di-n-heptylamine, di-n-octylamine, dicyclohexylamine, etc.; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri- n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, tri-n-dodecylamine, etc. Trialkylamine; alkanolamine such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, tri-n-octanolamine, etc. Among these, trialkylamine having 5 to 10 carbon atoms is more preferable, and tri-n-pentylamine or tri-n-octylamine is particularly preferable.

As a cyclic amine, a heterocyclic compound etc. which contain a nitrogen atom as a heteroatom are mentioned, for example. This heterocyclic compound may be monocyclic (aliphatic monocyclic amine) or polycyclic (aliphatic polycyclic amine). As aliphatic monocyclic amine, specifically, piperidine, piperazine, etc. are mentioned, for example. Aliphatic polycyclic amines are preferably those with 6 to 10 carbon atoms. Specifically, examples include: 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diaza Heterobicyclo[5.4.0]-7-undecene, hexamethyltetramine, 1,4-diazabicyclo[2.2.2]octane, etc.

Other aliphatic amines, such as: three (2-methoxymethoxyethyl) amine, three {2- (2-methoxyethoxy) ethyl} amine, three {2-(2 -Methoxyethoxymethoxy)ethyl}amine, tri{2-(1-methoxyethoxy)ethyl}amine, tri{2-(1-ethoxyethoxy)ethyl Base}amine, tri{2-(1-ethoxypropoxy)ethyl}amine, tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, triethanolamine Acetate, etc., preferably triethanolamine triacetate.

Moreover, aromatic amine can also be used for (D2) component. Aromatic amines, such as: 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or their derivatives, tribenzylamine, 2,6-diisopropylaniline, N-tert- Butoxycarbonylpyrrolidine, etc.

(D2) The component may be used individually or in combination of 2 or more types. When the resist composition contains (D2) component, (D2) component is normally used in the range of 0.01-5 mass parts with respect to 100 mass parts of (A) components. When it is in the above range, the balance with other components can be achieved, and various lithographic etching properties can be improved.

≪At least one compound (E) selected from the group consisting of organic carboxylic acids, phosphorus oxyacids and their derivatives≫ In the resist composition of this embodiment, for the purpose of preventing poor sensitivity, or improving resist pattern shape, storage stability (temporal stability) during processing, etc., organic carboxylic acid and phosphorus content may be contained as optional components. At least one compound (E) selected from the group consisting of oxyacids and their derivatives (hereinafter also referred to as "component (E)"). Organic carboxylic acids, for example: acetic acid, malonic acid, citrate, malic acid, succinic acid, benzoic acid, salicylic acid, etc. are preferred. Phosphorus oxyacids include, for example, phosphoric acid, phosphonic acid, and phosphine acid, among which phosphonic acid is particularly preferred. Derivatives of oxyacids of phosphorus include, for example, esters obtained by replacing the hydrogen atoms of the above-mentioned oxyacids with hydrocarbon groups. 15 Aryl, etc. Derivatives of phosphoric acid include, for example, phosphoric acid esters such as di-n-butyl phosphate and diphenyl phosphate. Examples of derivatives of phosphonic acid include phosphonate esters such as dimethyl phosphonate, di-n-butyl phosphonate, phenyl phosphonate, diphenyl phosphonate, and dibenzyl phosphonate. As a derivative of phosphinic acid, a phosphinic acid ester, phenyl phosphinic acid, etc. are mentioned, for example. (E) The component may be used individually by 1 type, and may use it in combination of 2 or more types. When the resist composition contains (E) component, (E) component is normally used in the range of 0.01-5 mass parts with respect to 100 mass parts of (A) components.

≪Fluorine additive component (F)≫ The resist composition of this embodiment may contain a fluorine additive component (hereinafter also referred to as "component (F)") for the purpose of imparting water repellency to the resist film or improving lithographic etching characteristics. (F) Components, for example: those recorded in JP 2010-002870, JP 2010-032994, JP 2010-277043, JP 2011-13569, JP 2011-128226 can be used Fluorine-containing polymer compounds. (F) As a component, the polymer etc. which have the structural unit (f1) represented by following formula (f1-1) more specifically are mentioned, for example. The above-mentioned polymer, more specifically, for example: a polymer (homopolymer) formed only by the structural unit (f1) represented by the following formula (f1-1); A copolymer of a structural unit (a1) having a large acid-decomposable group and the structural unit (f1); the structural unit (f1), a structural unit derived from acrylic acid or methacrylic acid, and the aforementioned structural unit (a1) Copolymers are preferred. Among them, preferred ones of the aforementioned structural units (a1) that can be copolymerized with the structural unit (f1) include, for example, structural units derived from 1-ethyl-1-cyclooctyl (meth)acrylate , a structural unit derived from 1-methyl-1-adamantyl (meth)acrylate, and the like.

[式中，R與前述為相同之內容，Rf¹⁰² 及Rf¹⁰³ 各別獨立表示氫原子、鹵素原子、碳數1～5之烷基或碳數1～5之鹵化烷基；Rf¹⁰² 及Rf¹⁰³ 可為相同亦可、相異亦可。nf¹ 為1～5之整數，Rf¹⁰¹ 為含有氟原子之有機基]。

[In the formula, R is the same as the above, and Rf ¹⁰² and Rf ¹⁰³ independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 5 carbons, or a halogenated alkyl group with 1 to 5 carbons; Rf ¹⁰² and Rf ¹⁰³ may be the same or different. nf ¹ is an integer of 1 to 5, and Rf ¹⁰¹ is an organic group containing fluorine atoms].

In the formula (f1-1), R to which the carbon atom at the α position is bonded is the same as described above. Also, R is preferably a hydrogen atom or a methyl group. In the formula (f1-1), the halogen atoms of Rf ¹⁰² and Rf ¹⁰³ include, for example, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., especially fluorine atoms are preferred. The alkyl group having 1 to 5 carbon atoms in Rf ¹⁰² and Rf ¹⁰³ is, for example, the same as the alkyl group having 1 to 5 carbon atoms in R above, and preferably methyl or ethyl. The halogenated alkyl groups of Rf ¹⁰² and Rf ¹⁰³ having 1 to 5 carbon atoms, specifically, a group obtained by substituting a part or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms with a halogen atom wait. The halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is particularly preferable. Among them, Rf ¹⁰² and Rf ¹⁰³ are preferably hydrogen atoms, fluorine atoms, or alkyl groups with 1 to 5 carbon atoms, preferably hydrogen atoms, fluorine atoms, methyl groups, or ethyl groups. In the formula (f1-1), nf ¹ is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2.

In formula (f1-1), Rf ¹⁰¹ is an organic group containing fluorine atoms, preferably a hydrocarbon group containing fluorine atoms. The hydrocarbon group containing fluorine atoms can be any of linear, branched or cyclic, and preferably has 1 to 20 carbons, more preferably 1 to 15 carbons, and 1 to 15 carbons. 10 is excellent. In addition, the hydrocarbyl group containing fluorine atoms is preferably fluorinated with more than 25% of the hydrogen atoms in the hydrocarbyl group, preferably more than 50% is fluorinated, and when more than 60% is fluorinated, it can improve The hydrophobicity of the resist film during immersion exposure is particularly good. Among them, Rf ¹⁰¹ is preferably a fluorinated hydrocarbon group with 1 to 6 carbons, trifluoromethyl, -CH ₂ -CF ₃ , -CH ₂ -CF ₂ -CF ₃ , -CH(CF ₃ ) ₂ , -CH ₂ -CH ₂ -CF ₃ and -CH ₂ -CH ₂ -CF ₂ -CF ₂ -CF ₂ -CF ₃ are particularly preferred.

(F) The weight average molecular weight (Mw) of the component (in terms of polystyrene in gel permeation chromatography) is preferably from 1,000 to 50,000, more preferably from 5,000 to 40,000, most preferably from 10,000 to 30,000. When it is below the upper limit of this range, when used as a resist, it can have sufficient solubility to the solvent for the resist, and when it is above the lower limit of this range, good water repellency can be produced on the surface of the resist. (F) The degree of dispersion (Mw/Mn) of the component is preferably 1.0-5.0, more preferably 1.0-3.0, most preferably 1.2-2.5.

(F) The component may be used individually by 1 type, and may use it in combination of 2 or more types. When the resist composition contains (F) component, (F) component is normally used in the ratio of 0.5-10 mass parts with respect to 100 mass parts of (A) components.

In the resist composition of this embodiment, mixed additives can be appropriately added according to the purpose, such as resins added to improve the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, and anti-oxidants. Halo agent, dye, etc.

≪Organic solvent component (S)≫ The resist composition of this embodiment can be obtained by dissolving the resist material in an organic solvent component (hereinafter, also referred to as “(S) component”). The (S) component should be able to dissolve various components used to form a uniform solution, and any component can be appropriately selected from known components conventionally used as solvents for chemically amplified resist compositions. For example: (S) component, such as: lactones such as γ-butyrolactone; acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentanone, methyl isoamyl ketone, 2-heptanone Ketones such as ketones; polyols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or diethylene glycol monoacetate Compounds having ester linkages such as propylene glycol monoacetate, monoalkyl ethers or monophenyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, and monobutyl ether of the aforementioned polyols or the aforementioned compounds having ester linkages Derivatives of polyols such as compounds with ether linkages [among them, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred]; dioxane, etc. Cyclic ethers, or methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethoxy Esters such as ethyl propionate; anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, butyl phenyl ether, ethylbenzene, diethylbenzene, Aromatic organic solvents such as amylbenzene, cumene, toluene, xylene, isopropyltoluene, and mesitylene, dimethylsulfoxide (DMSO), etc. Component (S) may be used alone or as a mixed solvent of two or more types. Among them, PGMEA, PGME, γ-butyrolactone, EL, and cyclohexanone are preferable.

Moreover, the mixed solvent which mixed PGMEA and a polar solvent can also be used. The addition ratio (mass ratio) can be properly determined after considering the compatibility between PGMEA and polar solvents, etc., preferably 1:9~9:1, more preferably 2:8~8:2 Within the range is better. More specifically, when mixing EL or cyclohexanone as a polar solvent, the mass ratio of PGMEA:EL or cyclohexanone is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. Also, when mixing PGME as a polar solvent, the mass ratio of PGMEA:PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, more preferably 3:7 to 7:3 . In addition, a mixed solvent of PGMEA, PGME, and cyclohexanone can also be used. Moreover, (S) component and others can also use the mixed solvent of at least 1 sort(s) selected from PGMEA and EL, and γ-butyrolactone. In this case, the mixing ratio is preferably 70:30 to 95:5 based on the mass ratio of the former to the latter.

The amount of component (S) used is not particularly limited, and can be appropriately set in accordance with the concentration that can be applied to the substrate, etc., and the thickness of the coating film. Generally, the (S) component is used so that the solid content concentration of the resist composition is 0.1-20% by mass, preferably within the range of 0.2-10% by mass.

In the resist composition of this embodiment, the (A) component is a resin component (A1) containing a structural unit (a0), and the (B) component is a compound (b) represented by the aforementioned general formula (b-1). -1), at least one selected from the group consisting of the compound (b-2) represented by the aforementioned general formula (b-2) and the compound (b-3) represented by the aforementioned general formula (b-3) ( (B1) ingredients). In the resist composition of the present embodiment, because any one of the (A1) component and (B1) component contains an aromatic ring in its structure, it is speculated that the interaction between the (A1) component and (B1) component can be improved. effect. Therefore, when forming a resist pattern using the resist composition of this embodiment, it is possible to properly control the diffusion of acid generated by exposure to the unexposed portion of the pattern (acid diffusion), so it is presumed that the resist pattern can be improved. the roughness.

(Resist Pattern Formation Method) The method for forming a resist pattern according to this embodiment includes: using the above-mentioned resist composition, forming a resist film on a support; exposing the above-mentioned resist film; and exposing the above-mentioned exposed resist film. The step of developing to form a resist pattern. One of the embodiments of the method for forming a resist pattern is, for example, a method for forming a resist pattern in the following manner.

First, apply the resist composition of the above-mentioned embodiment on the support body using a spin coater, for example, at a temperature of 80-150°C for 40-120 seconds, preferably 60-90°C. Baking in seconds (Post Apply Bake (PAB)) to form a resist film. Next, for example, use an exposure device such as an ArF exposure device, an electron beam drawing device, an EUV exposure device, etc., to perform exposure through a mask (mask pattern) that forms a specific pattern, or use an electron beam without a mask pattern. After selectively exposing the resist film by direct irradiation, drawing, etc., it is then baked for 40 to 120 seconds, preferably 60 to 90 seconds, at a temperature of 80 to 150°C. (Post Exposure Bake (PEB)) treatment. Next, development treatment is performed on the aforementioned resist film. The development process is carried out using an alkali developer in the alkali development process, and a developer containing an organic solvent (organic developer) in the solvent development process. After the development treatment, it is preferable to perform a washing treatment. In the washing process, it is better to use pure water for washing in the alkaline development process, and it is better to use a washing solution containing an organic solvent in the solvent development process. In the solvent development process, after the above-mentioned development treatment or washing treatment, supercritical fluid can be used to remove the developing solution or washing solution adhering to the pattern. After the developing treatment or after the washing treatment, drying treatment is performed. In addition, depending on the situation, a firing treatment (post-baking) may be performed after the above-mentioned development treatment. In this manner, a resist pattern can be formed.

The support is not particularly limited, and conventionally known ones can be used, for example, substrates for electronic parts, or those on which a specific wiring pattern is formed. More specifically, metal substrates such as silicon wafers, copper, chromium, iron, and aluminum, glass substrates, and the like are exemplified. For the material of the wiring pattern, for example, copper, aluminum, nickel, gold, etc. can be used. In addition, the support may be one in which an inorganic and/or organic film is provided on the above-mentioned substrate. Inorganic films include, for example, inorganic anti-reflective films (inorganic BARC). Examples of organic films include organic anti-reflective coatings (organic BARC) and organic films used as lower organic films in the multilayer resist method. Among them, the multilayer resist method refers to setting at least one layer of organic film (lower layer organic film) and at least one layer of resist film (upper layer resist film) on the substrate, and then using the resist pattern formed on the upper layer resist film The pattern is used as a mask to pattern the underlying organic film. According to this method, a pattern with a high aspect ratio can be formed. That is, in the multilayer resist method, since the required thickness of the lower organic film can be ensured, the resist film can be thinned and a fine pattern with a high aspect ratio can be formed. In the multilayer resist method, basically, it can be divided into a method having a two-layer structure of an upper resist film and a lower organic film (two-layer resist method), and a method in which a resist film is placed between the upper resist film and the lower organic film. A method of having a multilayer structure of more than three layers with one or more intermediate layers (metal thin film, etc.) (3-layer resist method).

The wavelength used for exposure is not particularly limited, but ArF excimer laser, KrF excimer laser, F ₂ excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron line), X-rays, soft X-rays, etc. The aforementioned resist composition is highly useful for KrF excimer laser, ArF excimer laser, EB or EUV, and has higher usefulness for ArF excimer laser, EB or EUV. When using EUV, it has extremely high practicality.

The exposure method of the resist film may be normal exposure (dry exposure) performed in an inert gas such as air or nitrogen, or liquid immersion exposure (Liquid Immersion Lithography). Liquid immersion exposure is to fill the gap between the resist film and the lens at the lowest position of the exposure device in advance with a solvent (immersion medium) having a higher refractive index than air, and then perform exposure in this state ( immersion exposure) exposure method. The immersion medium is preferably a solvent having a higher refractive index than air and a lower refractive index than the exposed resist film. The refractive index of the solvent is not particularly limited as long as it is within the aforementioned range. A solvent having a higher refractive index than air and a smaller refractive index than the aforementioned resist film, such as water, fluorine-based inert liquids, silicon-based solvents, hydrocarbon-based solvents, etc. Specific examples of fluorine-based inert liquids include fluorine-based compounds such as C ₃ HCl ₂ F ₅ , C ₄ F ₉ OCH ₃ , C ₄ F ₉ OC ₂ H ₅ , and C ₅ H ₃ F ₇ as main components. Liquids etc. preferably have a boiling point of 70-180°C, more preferably 80-160°C. When the fluorine-based inert liquid has a boiling point in the above-mentioned range, it is preferable that the medium used for immersion can be removed by a simple method after the exposure is completed. The fluorine-based inert liquid is preferably a perfluoroalkyl compound in which all the hydrogen atoms of the alkyl group are replaced by fluorine atoms. Specific examples of perfluoroalkyl compounds include perfluoroalkyl ether compounds, perfluoroalkylamine compounds, and the like. In addition, specifically, the aforementioned perfluoroalkane ether compounds include, for example, perfluoro(2-butyl-tetrahydrofuran) (boiling point 102° C.), and the aforementioned perfluoroalkane amine compounds include, for example: perfluorotributylamine ( boiling point 174°C), etc. As the immersion medium, it is preferable to use water from the viewpoints of cost, safety, environmental problems, wide applicability, and the like.

The alkaline developing solution used in the developing process of the alkaline developing process, for example: 0.1-10 mass % tetramethylammonium hydroxide (TMAH) aqueous solution etc. The organic solvent contained in the organic developer used in the developing process of the solvent developing process is only required to dissolve the (A) component (the (A) component before exposure), and it can be suitably prepared from known organic solvents. choose. Specifically, polar solvents such as ketone-based solvents, ester-based solvents, alcohol-based solvents, nitrile-based solvents, amide-based solvents, and ether-based solvents, hydrocarbon-based solvents, and the like are exemplified. Ketone solvents are organic solvents containing C-C(=O)-C in their structure. Ester solvents are organic solvents containing C-C(=O)-O-C in their structure. Alcoholic solvents are organic solvents containing alcoholic hydroxyl groups in their structures. "Alcoholic hydroxyl group" means a hydroxyl group bonded to a carbon atom in an aliphatic hydrocarbon group. Nitrile solvents are organic solvents containing nitrile groups in their structure. Amide-based solvents are organic solvents containing amide groups in their structure. Ether solvents are organic solvents containing C-O-C in the structure. Among the organic solvents, there are also organic solvents having a plurality of functional groups showing the characteristics of each of the above solvents in the structure, and in this case, the organic solvent is also a solvent type corresponding to any one of the functional groups contained therein. For example, diethylene glycol monomethyl ether corresponds to any one of alcohol-based solvents and ether-based solvents in the above classification. The hydrocarbon-based solvent is a hydrocarbon solvent that is composed of a hydrocarbon that may be halogenated and does not have a substituent other than a halogen atom. The halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferred. Among the above-mentioned organic solvents contained in the organic developer, polar solvents are preferred, and ketone-based solvents, ester-based solvents, and nitrile-based solvents are preferred.

Ketone solvents, such as: 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexane Ketone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, acetonyl acetone, ionone, diacetone alcohol, acetyl carbitol, acetophenone, methyl Kenaphthone, isophorone, propylene carbonate, γ-butyrolactone, methylpentanone (2-heptanone), etc. Among these, methylpentanone (2-heptanone) is preferable as a ketone-based solvent.

Ester solvents, such as: methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether Acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether Acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, 2-methyl Oxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl -3-methoxybutyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4 -propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3- Methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxy Amyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, carbonic acid Butyl ester, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, Isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3 - Ethoxypropionate, Propyl-3-methoxypropionate, etc. Among these, butyl acetate is preferable as an ester-based solvent.

Nitrile solvents, such as acetonitrile, propionitrile, valeronitrile, butyronitrile, etc.

To the organic developer, known additives may be added as necessary. The additives are, for example: surfactants and the like. The surfactant is not particularly limited, for example, ionic or nonionic fluorine-based and/or silicon-based surfactants can be used. The surfactant is preferably a non-ionic surfactant, and more preferably a non-ionic fluorine-based surfactant or a non-ionic silicon-based surfactant. When adding a surfactant, the amount added is usually 0.001-5% by mass, preferably 0.005-2% by mass, more preferably 0.01-0.5% by mass, relative to the total amount of the organic developer.

The development treatment can be carried out using known developing methods, for example: the method of immersing the support body in the developer solution for a specific time (immersion method), making the developer solution cover the surface of the support body according to the surface tension, and maintaining it in a static state for a specific time period Method (puddle method), method of spraying the developer on the surface of the support (spray method), spraying the developer from the nozzle that scans at a specific speed to the support that rotates at a specific speed The above method (Dynamicdispense method), etc.

In the solvent development process, the organic solvent contained in the washing solution used in the washing treatment after the development treatment, for example, can be appropriately selected from the organic solvents listed as the organic solvents for the organic system developing solution, and use a non-dissolving resist. Solvents for Dosage Graphics. Usually, at least one solvent selected from hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents is used. Among these, at least one selected from hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, and amide-based solvents is preferred, and at least one selected from alcohol-based solvents and ester-based solvents One type is preferred, and alcoholic solvents are particularly preferred. The alcohol-based solvent used in the cleaning solution is preferably a monohydric alcohol with 6 to 8 carbon atoms, and the monohydric alcohol may be linear, branched or cyclic. Specifically, examples include: 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3- Octanol, 4-octanol, benzyl alcohol, etc. Among these, 1-hexanol, 2-heptanol, and 2-hexanol are preferable, and 1-hexanol and 2-hexanol are more preferable. These organic solvents may be used either alone or in combination. Moreover, it can also use after mixing with the organic solvent other than the above, or water. However, when considering the development characteristics, the amount of water added to the washing solution is preferably not more than 30% by mass, more preferably not more than 10% by mass, more preferably not more than 5% by mass, based on the total amount of the cleaning solution. 3% by mass or less is particularly preferred. To the washing liquid, known additives may be added as necessary. The additives are, for example: surfactants and the like. Surfactants, for example: the same content as the above, etc., and preferably non-ionic surfactants, non-ionic fluorine-based surfactants, or non-ionic silicon-based surfactants good. When adding a surfactant, the amount thereof is usually 0.001-5% by mass, preferably 0.005-2% by mass, more preferably 0.01-0.5% by mass, relative to the total amount of the washing liquid.

The washing treatment (cleaning treatment) using a washing liquid can be carried out according to a known washing method. The method of washing treatment, for example: the method of continuously coating the washing liquid on the support rotating at a specific speed (rotary coating method), the method of immersing the support in the washing liquid for a specific time (dipping method), A method of spraying a cleaning solution on the surface of a support (spray method), etc.

In the resist pattern forming method of the present embodiment described above, since the resist composition of the above-mentioned first aspect is used, high sensitivity can be achieved when forming a resist pattern. In addition, according to the resist pattern forming method, the lithographic etching characteristics (resolution, roughness reduction, etc.) can be further improved, the resolution can be improved, and a resist pattern with a good shape can be formed. [Example]

Hereinafter, the present invention will be described in more detail with examples, but the present invention is not limited by these examples.

(Polymer Synthesis Example 1: Synthesis of Polymer P-1) 10.0 g of monomer (m101), 12.7 g of monomer (m01), and azobis(isobutyric acid) dimethyl ( V-601) 1.4 g was dissolved in 50.0 g of MEK (methyl ethyl ketone), heated to 85° C. under a nitrogen atmosphere, and stirred for 5 hours. Subsequently, 9.4 g of acetic acid and 160 g of methanol were added to the reaction solution, and a deprotection reaction was performed at 30° C. for 8 hours. After completion of the reaction, the obtained reaction liquid was precipitated in 2500 g of heptane and washed. The resulting white solid was filtered and dried under reduced pressure overnight to obtain 14.1 g of the target polymer compound P-1. The obtained polymer P-1 had a standard polystyrene-equivalent weight average molecular weight (Mw) of 6600 and a molecular weight dispersion (Mw/Mn) of 1.63 as determined by GPC. Also, the copolymerization composition ratio (ratio (molar ratio) of each structural unit in the structural formula) obtained by ¹³ C-NMR was 1/m=50/50.

(Polymer Synthesis Examples 2-5: Synthesis of Polymers P-2-P-5) The compounds shown in Table 1 were used in the molar ratio shown in Table 1, according to the same method as in Polymer Synthesis Example 1 , synthetic polymer P-2 ~ P-5. For the obtained polymers P-2 to P-5, according to the copolymerization composition ratio of the polymer compound obtained by ¹³ C-NMR (the ratio of each structural unit in the polymer compound (molar ratio)), Table 1 shows the mass average molecular weight (Mw) and molecular weight dispersion (Mw/Mn) obtained by GPC measurement in terms of standard polystyrene.

(Polymer Synthesis Example 6: Synthesis of Polymer P-6) 6.0 g of monomer (m101), 15.2 g of monomer (m01), 1.7 g of monomer (m21), and azobis( 1.4 g of isobutyric acid) dimethyl (V-601) was dissolved in 50.0 g of MEK (methyl ethyl ketone), heated to 85° C. under a nitrogen atmosphere, and stirred for 5 hours. Subsequently, 11.3 g of acetic acid and 190 g of methanol were added to the reaction liquid, and a deprotection reaction was performed at 30° C. for 8 hours. After completion of the reaction, the obtained reaction liquid was precipitated in 2500 g of heptane and washed. The resulting white solid was filtered and dried under reduced pressure overnight to obtain 13.2 g of the target polymer compound (P-6). The obtained polymer compound (P-6) had a standard polystyrene-equivalent weight average molecular weight (Mw) of 7,200 and a molecular weight dispersion (Mw/Mn) of 1.65 as measured by GPC. Also, the copolymerization composition ratio (ratio (molar ratio) of each structural unit in the structural formula) obtained by ¹³ C-NMR was 1/m/n=30/60/10.

(Polymer Synthesis Example 7: Synthesis of Polymer P-7) 6.0 g of monomer (m101), 15.2 g of monomer (m01), 2.3 g of monomer (m31), and azobis( 1.4 g of isobutyric acid) dimethyl (V-601) was dissolved in 50.0 g of MEK (methyl ethyl ketone), heated to 85° C. under a nitrogen atmosphere, and stirred for 5 hours. Subsequently, 11.3 g of acetic acid and 190 g of methanol were added to the reaction liquid, and a deprotection reaction was performed at 30° C. for 8 hours. After completion of the reaction, the obtained reaction liquid was precipitated in 2500 g of heptane and washed. The resulting white solid was filtered and dried under reduced pressure overnight to obtain 13.8 g of the target polymer compound (P-7). The obtained polymer compound (P-7) had a standard polystyrene-equivalent weight average molecular weight (Mw) of 7,000 and a molecular weight dispersion (Mw/Mn) of 1.67 as determined by GPC measurement. Also, the copolymerization composition ratio (ratio (molar ratio) of each structural unit in the structural formula) obtained from the carbon 13 nuclear magnetic resonance spectrum ( ^150MHz_13C -NMR) is l/m/n=30/60/10.

(Polymer Synthesis Examples 8-9: Synthesis of Polymers P-8-P-9) The compounds shown in Table 1 were used in the molar ratio shown in Table 1, according to the same method as in Polymer Synthesis Example 1 , synthetic polymer P-8 ~ P-9. For the obtained polymers P-8 to P-9, the copolymerization composition ratio of the polymer compound obtained by ¹³ C-NMR (the ratio of each structural unit in the polymer compound (molar ratio)), Table 1 shows the mass average molecular weight (Mw) and molecular weight dispersion (Mw/Mn) obtained by GPC measurement in terms of standard polystyrene.

(Polymer Synthesis Example 10: Synthesis of Polymer P-10) With the compounds shown in Table 1, using the molar ratio shown in Table 1, according to the same method as Polymer Synthesis Example 6, synthesize Polymer P-10 10. The obtained polymer P-10 was obtained according to the copolymerization composition ratio of the polymer compound obtained by ¹³ C-NMR (the ratio of each structural unit in the polymer compound (molar ratio)), and the ratio obtained by GPC measurement. Table 1 shows the obtained mass average molecular weight (Mw) and molecular weight dispersion (Mw/Mn) in terms of standard polystyrene.

(Polymer Synthesis Example 11: Synthesis of Polymer P-11) With the compounds shown in Table 1, using the molar ratio shown in Table 1, according to the same method as Polymer Synthesis Example 7, synthesize Polymer P-11 11. The obtained polymer P-11 was obtained according to the copolymerization composition ratio of the polymer compound obtained by ¹³ C-NMR (the ratio of each structural unit in the polymer compound (molar ratio)), and the ratio obtained by GPC measurement. Table 1 shows the obtained mass average molecular weight (Mw) and molecular weight dispersion (Mw/Mn) in terms of standard polystyrene.

＜Manufacture of resist composition＞ The ingredients shown in Tables 2 and 3 were mixed and dissolved to prepare the resist compositions of each example.

In Tables 2 and 3, each abbreviation has the following meanings respectively. The value in [ ] is the added amount (parts by mass). (A)-1 to (A)-11: the aforementioned polymers P-1 to P-11. (B)-1 to (B)-18: Acid generators represented by the following chemical formulas (B)-1 to (B)-18. (D)-1: an acid diffusion inhibitor represented by the following chemical formula (D)-1. (S)-1: A mixed solvent of propylene glycol monomethyl ether acetate/propylene glycol monomethyl ether=40/60 (mass ratio).

＜Evaluation of resist composition＞ A resist pattern was formed using the obtained resist composition, and various evaluations, such as sensitivity (Eop), resolution, and LWR, were performed as follows.

[Resist patterning] Use a spin coater to coat the resist composition of each example on a silicon substrate treated with hexamethyldisilazane (HMDS), and place it on a heating plate at a temperature of 110°C for 60 seconds After the pre-baking (PAB) treatment, it is dried to form a resist film with a film thickness of 50 nm. Next, using the electronic line drawing device JEOL-JBX-9300FS (manufactured by Japan Electronics Co., Ltd.), at an acceleration voltage of 100kV and a target size of 50nm in line width, a 1:1 line and space pattern (hereinafter also referred to as "LS") Pattern"), after drawing (exposure) the aforementioned resist film, a post-exposure heating (PEB) treatment was performed at 110° C. for 60 seconds. Next, after performing alkali development for 60 seconds at 23°C using a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution "NMD-3" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.), Rinse with pure water for 15 seconds. As a result, a 1:1 LS pattern with a line width of 50nm was formed.

[Evaluation of Optimum Exposure (Eop)] Calculate the optimum exposure Eop (μC/cm ² ) for forming an LS pattern with a target size according to the aforementioned resist patterning method. The results are shown in Tables 4 and 5.

[Analytical evaluation] Specifically, the critical resolution in the above-mentioned Eop is to use a scanning electron microscope S-9380 (manufactured by Hitachi High-Tech Co., Ltd.) to observe the LS pattern formed by gradually increasing the exposure amount starting from the optimal exposure amount Eop. In practice, the minimum size of a graph that is not collapsed and can be resolved. The results are shown in Tables 4 and 5.

[Evaluation of LWR (Line Wise Roughness)] For the LS pattern formed in the above [Formation of Resist Pattern], calculate the 3σ indicating the LWR scale. "3σ" is the standard deviation obtained from measuring the position of the line in the line length direction at 400 points using a scanning electron microscope (accelerating voltage 800V, product name: S-9380, manufactured by Hitachi High-Tech Co., Ltd.) The triple value (3σ) (unit: nm) of (σ) is marked as shown in Tables 4 and 5. The smaller the value of 3σ, the smaller the roughness of the line sidewall and the more uniform width of the LS pattern can be obtained.

From the results shown in Tables 5 and 6, it was confirmed that the resist compositions using Examples 1 to 18 of the present invention had good sensitivity, resolution and LWR as shown below. In the resist compositions of Comparative Examples 1 to 4, the (B) component was the same as in Example 1 except that R ¹⁰¹ in the formula (b-1) is a hydrocarbon group that does not contain an aromatic ring that may have a substituent. The resist compositions of ~9 have the same composition content. When the resist compositions of Examples 1-9 were compared with the resist compositions of Comparative Examples 1-4, it was confirmed that the sensitivity, resolution, and LWR were all improved. In the resist compositions of Comparative Examples 5 to 7, the components (B) were the same as those in Example 10, except that R ¹⁰¹ in the formula (b-1) was a hydrocarbon group that did not contain an aromatic ring that may have a substituent. The resist compositions of ~12 have the same composition content. When the resist compositions of Examples 10-12 were compared with the resist compositions of Comparative Examples 5-7, it was confirmed that the sensitivity, resolution and LWR were all improved. When the resist compositions of Examples 1 and 13 to 16 were compared with the resist compositions of Comparative Examples 8 and 9, which had the same composition except for the component (A), it was confirmed that both resolution and LWR were improved. In addition, it was confirmed that the resist compositions of Examples 1 and 13 to 16 had a sensitivity equal to or higher than that of the resist compositions of Comparative Examples 8 and 9. In the resist compositions of Comparative Examples 8 and 9, the (A) component was used except the polymerization of the structural unit (a0) corresponding to the structural unit (a0) in the (A) component of the resist compositions of Examples 1 and 13, respectively. Other than the resist compositions of Examples 1 and 13, the others have the same composition content. When the resist compositions of Examples 1 and 13 were compared with the resist compositions of Comparative Examples 8 and 9, it was confirmed that both resolution and LWR were improved. In addition, it was confirmed that the resist compositions of Examples 1 and 13 have sensitivities equivalent to or higher than those of the resist compositions of Comparative Examples 8 and 9, respectively. In the resist compositions of Comparative Examples 10 and 11, the (A) component, except for the polymerization of the structural unit (a0) corresponding to the structural unit (a0) in the (A) component of the resist compositions of Examples 17 and 18, was used. Except for the resist composition of Examples 17 and 18, the others have the same composition content. When the resist compositions of Examples 17 and 18 were compared with the resist compositions of Comparative Examples 10 and 11, it was confirmed that the sensitivity, resolution and LWR were all improved.

The above is to illustrate the preferred embodiments of the present invention, but the present invention is not limited by these embodiments. Additions, omissions, substitutions, and other changes of constituent contents are all possible within the scope not departing from the gist of the present invention. The present invention is not limited by the foregoing description, but only by the scope of the appended patent application.

Claims (4)

A resist composition, which is a resist composition that generates acid through exposure and changes the solubility of the developing solution through the action of the acid, comprising: The substrate component (A) that changes, and the acid generator component (B) that generates acid through exposure, and the aforementioned substrate component (A) contains a structural unit (a0) represented by the following general formula (a0) The resin component (A1), the acid generator component (B) contains a compound (b-1) represented by the following general formula (b-1), a compound (b-1) represented by the following general formula (b-2) -2) and at least one selected from the group consisting of compounds (b-3) represented by the following general formula (b-3);

[In the formula, R ⁰ is a hydrogen atom, an alkyl group with 1 to 5 carbons, a halogen atom or a halogenated alkyl group with 1 to 5 carbons; Va ^x0 is a single bond or a divalent linking group; Wa is an optional substituent A divalent aromatic hydrocarbon group; Va ⁰ is a divalent hydrocarbon group that may have an ether bond; n _a0 is an integer from 0 to 2; Ra ⁰⁰ is the acid dissociation represented by the following formula (a1-r-2) base];

[In the formula, Ra' ⁴ ~ Ra' ⁶ are each independently a hydroxyl group that may have a substituent, and Ra' ⁵ and Ra' ⁶ can be bonded to each other to form a ring];

[wherein, R ¹⁰¹ , R ¹⁰⁴ and R ¹⁰⁶ are each independently a hydrocarbon group containing an aromatic ring that may have a substituent; R ¹⁰⁵ , R ¹⁰⁷ and R ¹⁰⁸ are each independently a cyclic group that may have a substituent, A chained alkyl group that may have a substituent, or a chained alkenyl group that may have a substituent; R ¹⁰² is a fluorine atom or a fluorinated alkyl group with 1 to 5 carbon atoms; Y ¹⁰¹ is a single bond or a divalent group containing an oxygen atom V ¹⁰¹ ~ V ¹⁰³ are each independently a single bond, alkylene or fluorinated alkylene; L ¹⁰¹ ~ L ¹⁰² are each independently a single bond or an oxygen atom; L ¹⁰³ ~ L ¹⁰⁵ are each independently Single bond, -CO- or -SO ₂ -; m is an integer of 1 or more, and M' ^m+ is an m-valent onium cation]. The resist composition according to claim 1, wherein the aforementioned resin component (A1) still has a structural unit (a10) represented by the following general formula (a10-1);

[wherein, R is a hydrogen atom, an alkyl group with 1 to 5 carbons or a halogenated alkyl group with 1 to 5 carbons; Ya ^x1 is a single bond or a linking group with 2 valences; Wa ^x1 is a valence of (n _ax1 +1) aromatic hydrocarbon group; n _ax1 is an integer of 1 or more]. A method for forming a resist pattern, comprising: a step of forming a resist film on a support using the resist composition according to claim 1, a step of exposing the resist film, and exposing the exposed resist film to The step of developing to form a resist pattern. The method for forming a resist pattern according to claim 3, wherein in the step of exposing the resist film, the resist film is exposed using EUV (extreme ultraviolet light) or EB (electron beam).